Polymers based on benzodiones

ABSTRACT

The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula (I), and compounds of formula (III), wherein Y, Y 15 , Y 16  and Y 17  are independently of each other a group of formula (A), (B) or (C) and their use as IR absorber, organic semiconductor in organic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes.

The present invention relates to polymers comprising one or more(repeating) unit(s) of the formula (I), and compounds of formula (III)and their use as IR absorber, organic semiconductor in organic devices,especially in organic photovoltaics and photodiodes, or in a devicecontaining a diode and/or an organic field effect transistor. Thepolymers and compounds according to the invention can have excellentsolubility in organic solvents and excellent film-forming properties. Inaddition, high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability can beobserved, when the polymers and compounds according to the invention areused in organic field effect transistors, organic photovoltaics andphotodiodes.

WO2012/003918 relates to polymers comprising repeating units of formula

wherein X is O, S, or NR^(x). While copolymers, such as, for example,

are mentioned as preferred compounds, where a thiophenylen group isdirectly bonded to the isobenzo DPP basic structure, WO2012/003918 failsto disclose a method for the production of the corresponding isobenzoDPP monomers

which are necessary for the production of the copolymers. Examples 1 to4 of WO2012/003918 only disclose polymers having a phenylen groupdirectly bonded to the benzodifurandion basic skeleton. While thesynthesis of 3,7-dibromo-benzo[1,2-b;4,5-b]dithiophene-2,6-dione hasbeen described in Chemistry Letters (1983) 905-908, the extension tobisarylated derivatives as shown in scheme 3 of WO2012/003918 is a meretheoretical possibility, which has not been reduced to practice.

Kai Zhang and Bernd Tieke, Macromolecules 44 (2011) 4596-4599 relates toπ-conjugated monomers and polymers containing benzodifuranone units inthe main chain:

The polymers show very broad absorption bands with a high extinctioncoefficient up to 32-500 L mol⁻¹ cm⁻¹. The polymers also show reversibleredox behavior, giving small HOMO-LUMO gaps up to 1.30 eV with strongdonor-acceptor character.

Weibin Cui et al., Macromolecules 44 (2011) 7869-7873 describes thesynthesis of several benzodipyrrolidone-based small molecules.

Cpd. X R 3a H H 3b Br H 5a-1 H Methyl 5a-2 H Ethylhexyl 5b BrOctyldodecyl

Moreover, two benzodipyrrolidone-based low-band-gap conjugated polymerswere prepared by means of Suzuki coupling polymerization.

The band gaps were estimated to be 1.9 eV of PBDPDP-B and 1.68 eV ofPBDPDP-T. The synthesis of the symmetrical monomers requires thecondensation of 0.5 eq. hydroquinone and 1 eq. of a mandelic acidderivative, respectively, leading to a double cyclization ofbenzodihydrofuranone, followed by oxidation to the conjugatedbenzodifuranones. The synthesis of such symmetrical benzofuranedionesis, for example, described in Dyes and Pigments (1980), 1(2), 103-120.

EP0252406A2 describes a process for the preparation of dyes of theformula

where A and B are each O, S or N-alkyl, X₁ and X₂ are each H, halogen orhydrocarbon radicals, and Y₁ and Y₂ are each preferably aryl. Thecompounds described in the examples are characterized in that A and Bare —O— and at least one of Y₁ and Y₂ is an aryl group.

EP0574118A1 relates to benzodifuranone dyes carrying at least onethiazolyl group.

Among others benzodifuranone dyes of formula

are disclosed, wherein R is —H or alkyl; X is —H, alkyl oralkylcarbonyl; A is a phenyl group which is unsubstituted or substitutedby from one to three substituents; or A is a group of the formula

wherein R¹ is —H or alkyl; and X¹ is —H, alkyl or alkylcarbonyl.

WO9412577A2 relates to a process for the preparation of a polycyclic dyeof the Formula

wherein ring A is unsubstituted or is substituted by from 1 to 5 groups;ring B is unsubstituted or is substituted by from 1 to 5 groups; X andX¹ each independently is —H, halogen, cyano, alkyl or aryl.

The synthesis of the symmetrical monomers required the condensation of0.5 eq. hydroquinone and 1 eq. of a mandelic acid derivative,respectively, leading to a double cyclization of benzodihydrofuranone,followed by oxidation to the conjugated benzodifuranones.

It is one object of the present invention to provide polymers andcompounds, which show high efficiency of energy conversion, excellentfield-effect mobility, good on/off current ratios and/or excellentstability, when used in organic field effect transistors, organicphotovoltaics (solar cells) and photodiodes. Another object of theinvention is to provide polymers and compounds with very low band gap,which can also be used as infrared (IR) absorbers. Still another objectof the invention is to provide a new synthesis route to benzodiones with5-ring-heterocycles (instead of (substituted)phenyl) directly attachedto the benzodione basic structure to form structures where thebenzodione core and the directly attached 5-ring-heterocycles arearranged in a planar manner.

In a first aspect of the present invention, said object has been solvedby polymers, comprising one or more (repeating) unit(s) of the formula

Ar³_(c)Ar²_(b)Ar¹_(a)YAr^(1′)_(a′)Ar^(2′)_(b′)Ar^(3′)_(c′)(I), wherein Y is a group of formula

a is 1, 2, or 3, a′ is 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3;

U¹ is O, S, or NR¹; U² is O, S, or NR²;

T¹ and T² are independently of each other hydrogen, halogen, hydroxyl,cyano, —COOR¹⁰³, —OCOR¹⁰³, —NR¹¹²COR¹⁰³, —CONR¹¹²R¹¹³, —SOR^(103′),—SO₂R^(103′), —NR¹¹²SO₂R^(103′), —NR¹¹²R¹¹³, C₁-C₂₅alkyl, which may besubstituted by E and/or interrupted by D, C₅-C₁₂cycloalkyl, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy;C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G;R¹ and R² may be the same or different and are selected from hydrogen, aC₁-C₁₀₀alkyl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₃-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group;a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group;a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group, or—COO—C₁-C₁₈alkyl group;R³⁹ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, orC₁-C₁₈alkanoyl,R¹⁰³ and R^(103′) are independently of each other C₁-C₁₀₀alkyl,especially C₃-C₂₅alkyl, C₁-C₂₅alkyl substituted by E and/or interruptedwith D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G,Ar¹ and Ar^(1′) are independently of each other

such as, for example,

such as, for example,

whereinX is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

Ar², Ar^(2′), Ar³ and Ar^(3′) have independently of each other themeaning of Ar¹, or are independently of each other

such as, for example,

such as, for example,

wherein X¹ is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—,—C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano,COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₂₄aryl or C₂-C₂₀heteroaryl,R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are independently of each otherhydrogen, halogen, halogenated C₁-C₂₅alkyl, especially CF₃, cyano,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₂₅alkoxy;R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen,C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one, or more oxygen, or sulphur atoms; or C₇-C₂₅arylalkyl,R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,R¹¹ and R^(11′) are independently of each other C₁-C₂₅alkyl group,especially a C₁-C₈alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy;R¹² and R^(12′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or =—R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or atri(C₁-C₈alkyl)silyl group;R¹⁰⁴ and R^(104′) are independently of each other hydrogen, C₁-C₁₈alkyl,C₆-C₁₀aryl, which may optionally be substituted by G, orC₂-C₈heteroaryl, which may optionally be substituted by G,R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₁₈alkoxy,R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl;C₁-C₂₅alkyl; especially C₃-C₂₅alkyl, which may be interrupted by —O—, or—S—; or —COOR¹⁰³; R¹⁰³ is as defined above;R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl,C₁-C₂₅alkyl which is substituted by E and/or interrupted by D,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, orR¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, whereinR¹¹⁰ and R¹¹¹ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, orR¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR¹¹²—,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, orhalogen,G is E, or C₁-C₁₈alkyl, andR¹¹² and R¹¹³ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R¹¹⁴ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms,R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or =—R¹¹⁶, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or atri(C₁-C₈alkyl)silyl group;R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group,especially a C₁-C₈alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy;R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen,halogen, halogenated C₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl,especially C₃-C₂₅alkyl, which may optionally be interrupted by one ormore oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;R¹²² and R^(122′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl. Polymers,comprising a repeating unit of the formula (I), are preferred. Thesemiconducting polymers of the present invention are conjugated.

If Y is a group of formula

a is 1, a′ is 1, b is 0, b′ is 0, c is 0 and c′ is 0; T¹ and T² arepreferably a hydrogen atom, U¹ is preferably NR¹ and U² is preferablyNR².

If Y is a group of formula

Ar¹ and Ar^(1′) are preferably independently of each other a group offormula XIa, XIb, XIc, XIe, XIf, XIl, XIp, XIr, XIs, XIx, XIIf, XIIg,XIIIa, XIIId, or XIIIl, especially XIb, XIc, XIe, XIf, XIl, XIp, XIr,XIs, XIx, XIIf, XIIg, XIIIa, XIIId, or XIIIl, very especially XIf,

Groups of formula

are preferred, wherein T¹ and T² are a hydrogen atom, U¹ is NR¹ and U²is NR².R¹ and R² are preferably selected from hydrogen, a C₁-C₁₀₀alkyl groupwhich can optionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or can optionally be interrupted by—O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₃-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl;a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl;a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group, or—COO—C₁-C₁₈alkyl group.

In a preferred embodiment Ar¹ and Ar^(1′) are independently of eachother a group of formula (XIa), (XIb), (XIc), (XId), (XIe), (XIf),(XIg), (XIh), (XIi), (XIj), (XIk), (XIl), (XIm), (XIn), (XIo), (XIp),(XIq), (XIr), (XIs), (XIt), (XIu), (XIv), (XIw), (XIx), (XIy), (XIz),(XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi),(XIIj), (XIIk), (XIIl), such as, for example, (XIIIa), (XIIIb), (XIIIc),(XIIId), (XIIIe), (XIIIf), (XIIIg), (XIIIh), (XIIIi), (XIIIj), (XIIIk);and (XIIIl), or (XIV), such as, for example, (XIVa). In preferredembodiment Ar¹ and Ar^(1′) are independently of each other a group offormula (XIVb), (XIVc), (XIVd), or (XIVe), especially (XIVb), (XIVc), or(XIVd), very especially (XIVb), or (XIVc).

In a second aspect of the present invention, said object has been solvedby compounds of formula (III), which are described in more detail below.

Advantageously, the polymer, or compound of the present invention, or anorganic semiconductor material, layer or component, comprising thepolymer, or compound of the present invention can be used in organicphotovoltaics (solar cells), photodiodes, in an organic field effecttransistor (OFET), as IR absorber, in thin film transistors (TFT),intergrated circuits (IC), radio frequency identification (RFID) tags,devices or components, organic light emitting diodes (OLED), organiclight emitting transistors (OLET), flat panel displays, backlights ofdisplays, laser diodes, photoconductors, photodetectors,electrophotographic devices, electrophotographic recording devices,organic memory devices, sensor devices, charge injection layers, chargetransport layers or interlayers in polymer light emitting diodes(PLEDs), organic plasmon emitting diodes (OPEDs), Schottky diodes,planarising layers, antistatic films, polymer electrolyte membranes(PEM), conducting substrates, conducting patterns, electrode materialsin batteries, alignment layers, biosensors, biochips, security markings,security devices, and components or devices for detecting anddiscriminating DNA sequences.

The polymers of this invention preferably have a weight averagemolecular weight of 4,000 Daltons or greater, especially 4,000 to2,000,000 Daltons, more preferably 10,000 to 1,000,000 and mostpreferably 10,000 to 100,000 Daltons. Molecular weights are determinedaccording to high-temperature gel permeation chromatography (HT-GPC)using polystyrene standards. The polymers of this invention preferablyhave a polydispersity of 1.01 to 10, more preferably 1.1 to 3.0, mostpreferred 1.5 to 2.5. The polymers of the present invention arepreferably conjugated.

Oligomers of the present invention preferably have a weight averagemolecular weight below 4,000 Daltons.

In an embodiment of the present invention the polymer is a polymer offormula

wherein n is usually in the range of 4 to 1000, especially 4 to 200,very especially 5 to 150.

U¹ is preferably O or NR¹; more preferably NR¹.

U² is preferably O or NR¹; more preferably NR¹.

Preferably T¹ and T² are independently of each other hydrogen, halogen,cyano, —COOR¹⁰³, —OCOR¹⁰³, OR^(103′), C₁-C₂₅alkyl, which may besubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G;

More preferably, T¹ and T² are independently of each other hydrogen,halogen, cyano, —COOR¹⁰³, —OCOR¹⁰³, —OR¹⁰³, or C₁-C₂₅alkyl, which may besubstituted by E and/or interrupted by D; more preferably hydrogen,halogen, cyano, —OR¹⁰³, C₁-C₂₅alkyl. Most preferred T¹ and T² arehydrogen, or C₁-C₂₅alkyl, especially hydrogen.

In the definition of R¹ and R² a silyl group or a siloxanyl group means—SiR¹⁶¹R¹⁶²R¹⁶³, or —O—SiR¹⁶¹R¹⁶²R¹⁶³.

R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other hydrogen,C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substitutedwith C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶,—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy,NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted1 to 3 times by C₁-C₂₄ alkyl, halogen, cyano or C₁-C₂₅alkoxy; preferablyhydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally besubstituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl,—O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —O—(SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ or phenyl; more preferablyC₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted withC₁-C₄alkyl; C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶,—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ or phenyl; most preferably C₁-C₈alkyl,C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one, or moretimes with fluorine atoms; —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶ or—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶.

R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other hydrogen,C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substitutedwith C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹,—(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy,NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted1 to 3 times by C₁-C₂₄ alkyl, halogen, cyano or C₁-C₂₅alkoxy; preferablyhydrogen, C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl,—O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; more preferablyC₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹,—(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; most preferably C₁-C₈alkyl,C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one or moretimes with fluorine atoms; —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹ or—(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹.

R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ are independently of each other hydrogen,C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substitutedwith C₁-C₄alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃,C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy,phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₅alkyl,halogen, cyano, or C₁-C₂₅alkoxy; preferably hydrogen, C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃, or phenyl; more preferablyC₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; mostpreferably C₁-C₈alkyl, C₁-C₈haloalkyl, especially C₁-C₈alkyl which issubstituted one or more times with fluorine atoms; or —O—Si(CH₃)₃.

d is an integer from 1 to 50, preferably 1 to 40, even more preferably 1to 30, still more preferably 1 to 20, more preferably 1 to 15, stillmore preferably 1 to 10 and even more preferably 1 to 5 and mostpreferably 1 to 3.

R¹⁶⁷ and R¹⁶⁸ are independently of each other hydrogen, C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, C₃-C₂₅alkenyl, or phenyl; preferably C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, or phenyl; most preferably C₁-C₂₅alkyl.

In a particularly preferred embodiment R¹⁶¹, R¹⁶² and R¹⁶³ areindependently of each other C₁-C₂₅alkyl, especially C₁-C₈alkyl;C₁-C₂₅haloalkyl, especially C₁-C₈haloalkyl, such as, for example, —CF₃,—(CH₂)₂CF₃, —(CH₂)₂(CF₂)₅CF₃ and —(CH₂)₂(CF₂)₆CF₃; C₂-C₂₅alkenyl,especially C₂-C₈alkenyl; C₃-C₁₂cycloalkyl, especially C₅-C₆cycloalkyl,which might optionally be substituted with C₁-C₄alkyl; phenyl,—O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, or —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶. In case of a group—O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each otherC₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, or phenyl. In case of a group—(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶R¹⁶⁴ and R¹⁶⁵ are independently of each otherC₁-C₈alkyl, R¹⁶⁶ is C₁-C₈alkyl, or phenyl and d is an integer of 2 to 5.

Examples of groups of formula —SiR¹⁶¹R¹⁶²R¹⁶³, or —O—SiR¹⁶¹R¹⁶²R¹⁶³ areshown below:

(*- indicates the bond to the carbon atom, to which the silyl group orsiloxanyl group is connected).

R¹ and R² may be the same or different and are preferably selected fromhydrogen, a C₁-C₁₀₀alkyl group which can optionally be substituted oneor more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interruptedby —O—, —S—, —COO— or —OCO—,

a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,a C₄-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl,a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, and—COO—C₁-C₁₈alkyl.

More preferably R¹ and R² are selected from hydrogen, C₁-C₅₀alkyl,C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl,allyl, C₅-C₁₂cycloalkyl, phenyl, or naphthyl which can optionally besubstituted one or more times with C₁-C₁₂alkyl or C₁-C₁₂alkoxy,—CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl and —COO—C₁-C₁₈alkyl. Even morepreferably R¹ and R² are a C₁-C₅₀alkyl group. Still more preferably R¹and R² are a C₁-C₃₆alkyl group, such as, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl,n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,especially n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,2-ethylhexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl,2-decyl-tetradecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl,or tetracosyl. Preferably R¹ and R² have the same meaning.

Advantageously, the groups R¹ and R² can be represented by formula

wherein m1=n1+2 and m1+n1≧24. Chiral side chains, such as R¹, R²,R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*), can either behomochiral, or racemic, which can influence the morphology of thecompounds.

Preferably, R¹⁰³ and R^(103′) are independently of each otherC₁-C₂₅alkyl, C₁-C₂₅alkyl substituted by halogen, C₇-C₂₅arylalkyl, orphenyl; more preferably C₁-C₂₅alkyl.

Preferably Ar¹ and Ar^(1′) are independently of each other a group offormula XIa, XIb, XIc, XIe, XIf, XIl, XIp, XIr, XIs, XIx, XIIf, XIIg,XIIIa, XIIId, or XIIIl; more preferably a group of formula XIa, XIb,XIe, XIf, XIr, XIx, or XIIIa, still more preferably a group of formulaXIa, XIb, or XIf, most preferred a group of formula XIa, or XIf, veryespecially XIa.

Preferably, R³ and R^(3′) are independently of each other hydrogen,halogen, CF₃, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; more preferably CF₃,cyano or C₁-C₂₅alkyl; most preferred hydrogen, or C₁-C₂₅alkyl.

Preferably, R¹⁰⁴ and R^(104′) are independently of each other hydrogen,cyano or a C₁-C₂₅alkyl group, more preferably hydrogen, or a C₁-C₂₅alkylgroup, most preferred hydrogen.

Preferably, R⁴, R^(4′), R⁵, R^(5′), R⁶ and R^(6′) are independently ofeach other hydrogen, halogen, CF₃, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy,more preferably hydrogen, CF₃, cyano or C₁-C₂₅alkyl; most preferredhydrogen, or C₁-C₂₅alkyl.

Preferably R⁷, R^(7′), R⁹ and R^(9′) are independently of each otherhydrogen, C₁-C₂₅alkyl, more preferably C₄-C₂₅alkyl.

Preferably, R⁸ and R^(8′) are independently of each other hydrogen,C₁-C₂₅alkyl, C₁-C₂₅alkyl, which may optionally be interrupted by one ormore oxygen or sulphur atoms; or C₇-C₂₅arylalkyl, more preferablyhydrogen, or C₁-C₂₅alkyl.

Preferably, R¹¹ and R^(11′) are independently of each other aC₁-C₂₅alkyl group, especially a C₁-C₈alkyl group, or phenyl; morepreferably a C₁-C₈alkyl group.

Preferably, R¹² and R^(12′) are independently of each other hydrogen,C₁-C₂₅alkyl, C₁-C₂₅alkoxy, or =—R¹³, wherein R¹³ is a C₁-C₁₀alkyl group,or a tri(C₁-C₈alkyl)silyl group, more preferably hydrogen, C₁-C₂₅alkyl,or C₁-C₂₅alkoxy.

Preferably, Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) haveindependently of each other the meaning of Ar¹, or are independently ofeach other a group of formula XVa, XVb, XVc, XVIa, XVIb, XVIIa, orXVIIb, have more preferably independently of each other the meaning ofAr¹, or are independently of each other a group of formula XVa, XVb,XVc, XVIa, or XVIb. Among groups of formula XVa, XVb, XVc, XVIa, orXVIb, a group of formula XVa, or XVb is more preferred. If Ar², Ar^(2′),Ar³, Ar^(3′), Ar⁴ and Ar^(4′) have the meaning of Ar¹, preferably thesame preferences as for Ar¹ apply.

Preferably, R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of eachother hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₁₈alkoxy, morepreferably C₁-C₂₅alkyl or C₁-C₁₈alkoxy, most preferred hydrogen, orC₁-C₂₅alkyl.

R¹⁰⁷ is preferably hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen or sulphur atoms; orC₇-C₂₅arylalkyl, more preferably hydrogen, or C₁-C₂₅alkyl, mostpreferred C₄-C₂₅alkyl.

Preferably, R¹⁰⁸ and R¹⁰⁹ are independently of each other H,C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted byD, C₇-C₂₅arylalkyl, C₂-C₁₈alkenyl, or C₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹together form a five or six membered ring, which optionally can besubstituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, D is—CO—, —COO—, —S— or —O—, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN orhalogen, G is E, or C₁-C₁₈alkyl. More preferably, R¹⁰⁸ and R¹⁰⁹ areindependently of each other H, C₁-C₂₅alkyl or C₇-C₂₅arylalkyl. Mostpreferred R¹⁰⁸ and R¹⁰⁹ are independently of each other H, orC₁-C₂₅alkyl.

D is preferably —CO—, —COO—, —S— or —O—, more preferably —COO—, —S— or—O—, most preferred —S— or —O—.

Preferably, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, or halogen, morepreferably C₁-C₈alkoxy, CN, or halogen, most preferred halogen,especially F.

Preferably, R¹¹² and R¹¹³ are independently of each other H;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, more preferablyH, or C₁-C₁₈alkyl; most preferred C₁-C₁₈alkyl.

Y is preferably a group of formula

more preferably a group of formula

U¹ and U² are preferably O, more preferably NR¹. T¹ and T² are hydrogen,CN, or COOR¹⁰³, more preferably hydrogen.

In a preferred embodiment the present invention is directed to polymerscomprising one or more (repeating) unit(s) of the formula

*⇓Ar¹_(a)YAr^(1′)_(a′)* (I′), wherein Y is a group of formula

U¹ is O, S, or NR¹; U² is O, S, or NR²,

T¹ and T² may be different, but are preferably the same and arepreferably independently of each other hydrogen, halogen, cyano,—COOR¹⁰³, —OCOR¹⁰³, —OR¹⁰³, —SR¹⁰³, C₁-C₂₅alkyl, which may besubstituted by E and/or interrupted by D; more preferably hydrogen,halogen, cyano, —OR¹⁰³, or C₁-C₂₅alkyl; most preferred hydrogen, orC₁-C₂₅alkyl, especially hydrogen;R¹ and R² may be different, but are preferably the same are preferablyselected from hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl,C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl, C₅-C₁₂cycloalkyl, phenyl andnaphthyl, which can optionally be substituted one or more times withC₁-C₁₂alkyl or C₁-C₁₂alkoxy, —CO—C₅-C₁₂cycloalkyl and —COO—C₁-C₁₈alkyl;more preferably C₁-C₅₀alkyl; most preferred C₁-C₃₈alkyl group;a is 1, 2, or 3, a′ is 1, 2, or 3; wherein Ar¹ and Ar^(1′) are asdefined above; and R¹⁰³, D and E are as defined above.

In said embodiment Y is preferably a group of formula

U¹ and U² may be different, but are preferably the same. U¹ ispreferably O or NR¹; more preferably NR¹. U² is preferably O or NR¹;more preferably NR¹. Polymers, comprising a repeating unit of theformula (I′), are preferred.

T¹ and T² may be different, but are preferably the same. T¹ and T² arepreferably independently of each other hydrogen, halogen, cyano,—COOR¹⁰³, —OCOR¹⁰³, —OR¹⁰³, —SR¹⁰³, C₁-C₂₅alkyl, which may besubstituted by E and/or interrupted by D; more preferably hydrogen,halogen, cyano, —OR¹⁰³, or C₁-C₂₅alkyl; most preferred hydrogen, orC₁-C₂₅alkyl, very especially hydrogen.

R¹ and R² may be different, but are preferably the same. More preferablyR¹ and R² are selected from hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl,C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl,C₅-C₁₂cycloalkyl, phenyl, or naphthyl which can optionally besubstituted one or more times with C₁-C₁₂alkyl or C₁-C₁₂alkoxy,—CO—C₅-C₁₂cycloalkyl and —COO—C₁-C₁₈alkyl. More preferably R¹ and R² areC₁-C₅₀alkyl group. Most preferred R¹ and R² are a C₁-C₃₈alkyl group.

a and a′ may be different, but are preferably the same. a and a′ arepreferably 1, or 2, more preferably 1.

Ar¹ and Ar^(1′) may be different, but are preferably the same.Preferably, Ar¹ and Ar^(1′) are independently of each a group of formulaXIa, XIb, XIc, XIe, XIf, XIl, XIp, XIr, XIs, XIx, XIIf, XIIg, XIIIa,XIIId, or XIIIl (as defined above). More preferably, Ar¹ and Ar^(1′) area group of formula XIa, XIb, XIe, XIf, XIr, XIx, or XIIIa. Still morepreferably Ar¹ and Ar^(1′) are a group of formula XIa, XIb, or XIf. Mostpreferred Ar¹ and Ar^(1′) are a group of formula XIa, or XIf, especiallyXIa.

In a further preferred embodiment the present invention is directed topolymers, comprising one or more (repeating) unit(s) of the formula

whereinU¹ is O, or NR¹; preferably NR¹;U² is O, or NR²; preferably NR²;T¹ and T² are independently of each other hydrogen, or C₁-C₂₅alkyl,especially hydrogen;R¹ and R² may be the same or different and are selected from aC₁-C₃₈alkyl group, especially C₈-C₃₆alkyl group;R³ and R^(3′) are independently of each other hydrogen or C₁-C₂₅alkyl;andR⁸ and R^(8′) are independently of each other hydrogen or C₁-C₂₅alkyl,especially C₁-C₂₅alkyl. Polymers, comprising a repeating unit of theformula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), or (Ij),especially (Ia), (Ib), (Id), (Ie) or (Ih); are preferred.

Repeating unit(s) of the formula (Ia), (Ib), (Id), (Ie), (If), or (Ih),especially (Ia), (Ib), or (Id), are preferred; repeating unit(s) of theformula (Ia), (Ib), (Id), (Ie) or (Ih), especially (Ia), or (Id), aremore preferred; repeating unit(s) of the formula (Ia) are mostpreferred. In another preferred embodiment repeating) unit(s) of theformula (Ii) are preferred.

Preferably U¹ and U² are the same.

Preferably T¹ and T² are the same.

In another embodiment the present invention is directed to polymers,comprising (repeating) unit(s) of the formula *A* and *COM¹*,wherein

A is a repeating unit of formula (I), and—COM¹- is a repeating unit, which has the meaning of Ar², wherein Ar²are as defined above, or a group of formula*Ar¹⁴_(s)Ar¹⁵_(t)Ar¹⁶_(u)Ar¹⁷_(v)*,s is 1, t is 1, u is 0, or 1, v is 0, or 1, andAr¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are independently of each other a group offormula

wherein one of X⁵ and X⁶ is N and the other is CR¹⁴, andR¹⁴, R^(14′), R¹⁷ and R^(17′) are independently of each other H, or aC₁-C₂₅alkyl group.

Preferably Ar¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are independently of each other agroup of formula

most preferably

Examples of repeating units —COM¹- are groups of formula XIa, XIb, XIc,XIe, XIf, XIl, XIp, XIr, XIs, XIx, XIIf, XIIg, XIIIa, XIIId, XIIIl, XVa,XVb, XVc, XVIa, XVIb, XVIIa, or XVIIb. Among these groups of formulaXIa, XIb, XIe, XIf, XIr, XIx, XIIIa, XVa, XVb, XVc, XVIa, or XVIb arepreferred, groups of formula XIa, XIb, XIf, XVa, or XVb are morepreferred, groups of formula XIa, XIf, or XVa are still more preferred.Groups of formula XIa are most preferred. Additional examples ofrepeating units —COM¹- are groups of formula XIVb, XIVc, or XIVd,especially XIVb.

Examples of a group of formula*Ar¹⁴_(k)Ar¹⁵_(l)Ar¹⁶_(r)Ar¹⁷_(z)*, are

In a particularly preferred embodiment the repeating unit —COM¹- is agroup of formula

where R³ and R^(3′) are independently of each other hydrogen, orC₁-C₂₅alky, R¹⁰⁴ and R^(104′) preferably are independently of each otherhydrogen, cyano or a C₁-C₂₅alkyl group, and R¹⁴ and R¹⁴ areindependently of each other H, or a C₁-C₂₅alkyl group, especially aC₆-C₂₅alkyl, which may optionally be interrupted by one or more oxygenatoms.

In another preferred embodiment the repeating unit —COM¹- is a group offormula

whereinR⁴ and R⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group;R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl; andR¹⁰⁷ is C₁-C₂₅alkyl.

In a preferred embodiment of the present invention the polymer is acopolymer, comprising repeating units of formula *ACOM¹*, (VII),especially a copolymer of formula

wherein A and COM¹ are as defined above; n is number which results in amolecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000to 1,000,000 and most preferably 10,000 to 100,000 Daltons. n is usuallyin the range of 4 to 1000, especially 4 to 200, very especially 5 to150.

In a preferred embodiment the present invention is directed to polymers,wherein A is a repeating unit of formula (Ia), (Ib), (Id), or (Ii),especially (Ia), (Ib), or (Id), very especially (Ia), or (Id) (asdefined in claim 3); and *COM¹* is a group of formula

where R³ and R^(3′) are independently of each other hydrogen, orC₁-C₂₅alky, R¹⁰⁴ and R^(104′) are independently of each other hydrogen,cyano or a C₁-C₂₅alkyl group, and R¹⁴ and R¹⁴ are independently of eachother H, or a C₁-C₂₅alkyl group, especially a C₆-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen atoms.

In another preferred embodiment the present invention is directed topolymers, wherein A is a repeating unit of formula (Ia), (Ib), (Id), or(Ii), especially (Ia), (Ib), or (Id), very especially (Ia), or (Id) (asdefined in claim 3), and *COM¹* is a group of formula

whereinR⁴ and R⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group;R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl; andR¹⁰⁷ is C₁-C₂₅alkyl.

Among the polymers of formula I the following polymers are preferred:

whereinn is 4 to 1000, especially 4 to 200, very especially 5 to 100,R¹ is a C₁-C₃₈alkyl group, especially C₈-C₃₆alkyl group,R³, R^(3″) and R^(3′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especially hydrogen or C₁-C₂₅alkyl;R⁴ and R⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group;R⁷ and R^(7′) are independently of each otherR¹⁴ and R^(14′) are independently of each other independently of eachother hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl;R¹⁷ and R^(17′) are independently of each other H, or a C₁-C₂₅alkylgroup;R¹⁰³ is C₁-C₂₅alkyl,R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano,COOR¹⁰³, C₁-C₂₅alkyl, especially hydrogen or cyano;R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each otherhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especiallyhydrogen or C₁-C₂₅alkyl; andR¹⁰⁷ is C₁-C₂₅alkyl.

According to an embodiment of the present invention polymers of formula(Ia-1), (Ia-2), (Ia-3), (Ia-4), (Ia-5), (Ia-6), (Ia-7), (Ia-8) and(Ia-9) are preferred. According to another embodiment of the presentinvention polymers of formula (Ia-10), (Ia-11), (Ia-12), (Ia-13),(Ia-14), (Ia-15), (Ia-16), (Ia-17), (Ia-18), (Ia-19), (Ia-20), (Ia-21),(Ia-22), (Ia-23), (Ia-24), (Ia-25), (Ia-26), (Ia-27), and (Ia-27) arepreferred. Examples of particular preferred polymers are shown below:

wherein n is usually in the range of 4 to 1000, especially 4 to 200,very especially 5 to 150.

The polymers of the present invention can comprise more than 2 differentrepeating units, such as, for example, repeating units A, B and D, whichare different from each other. If the polymers comprise repeating unitsof the formula A-D* and B-D*, they are preferably (random)copolymers of formula *A-D*_(x)B-D*_(y)*, wherein x=0.995 to 0.005,y=0.005 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and whereinx+y=1. A is a repeating unit of formula (I), D* is a repeating unit—COM¹- and B is a repeating unit —COM¹-, or a repeating unit of formula(I); with the proviso that A, B and D* are different from each other.

Copolymers of formula VII can be obtained, for example, by the Suzukireaction. The condensation reaction of an aromatic boronate and ahalogenide, especially a bromide, commonly referred to as the “Suzukireaction”, is tolerant of the presence of a variety of organicfunctional groups as reported by N. Miyaura and A. Suzuki in ChemicalReviews, Vol. 95, pp. 457-2483 (1995). Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(11)acetates,tri-alykl-phosphonium salts/palladium (0) derivatives andtri-alkylphosphine/palladium (0) derivatives. Especially preferredcatalysts are 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate and, tri-tert-butylphosphoniumtetrafluoroborate ((t-Bu)₃P*HBF4)/tris(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) and tri-tert-butylphosphine(t-Bu)₃P/tris(dibenzylideneacetone)dipalladium (0) (Pd₂(dba)₃). Thisreaction can be applied to preparing high molecular weight polymers andcopolymers.

To prepare polymers corresponding to formula VII a dihalogenide offormula X¹⁰-A-X¹⁰ is reacted with an (equimolar) amount of a diboronicacid or diboronate corresponding to formula X¹¹COM¹X¹¹; or adihalogenide of formula X¹⁰COM¹X¹⁰ is reacted with an (equimolar)amount of a diboronic acid or diboronate corresponding to formulaX¹¹-A-X¹¹, wherein X¹⁰ is halogen, especially Br, or I; and X¹¹ isindependently in each occurrence —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY¹⁰Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹,Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, under the catalytic action of Pd andtriphenylphosphine. The reaction is typically conducted at about 0° C.to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene.Other solvents such as dimethylformamide, dioxane, dimethoxyethan andtetrahydrofuran can also be used alone, or in mixtures with an aromatichydrocarbon. An aqueous base, preferably sodium carbonate orbicarbonate, potassium phosphate, potassium carbonate or bicarbonate isused as activation agent for the boronic acid, boronate and as the HBrscavenger. A polymerization reaction may take 0.2 to 100 hours. Organicbases, such as, for example, tetraalkylammonium hydroxide, and phasetransfer catalysts, such as, for example TBAB, can promote the activityof the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int.Ed. Eng. 42 (2003) 1407 and references cited therein). Other variationsof reaction conditions are given by T. I. Wallow and B. M. Novak in J.Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G.Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Control ofmolecular weight is possible by using either an excess of dibromide,diboronic acid, or diboronate, or a chain terminator.

According to the process described in WO2010/136352 the polymerisationis carried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and anorganic phosphine or phosphonium compound,b) a base,c) a solvent or a mixture of solvents, characterized in thatthe organic phosphine is a trisubstituted phosphine of formula

or phosphonium salt thereof, wherein X″ independently of Y″ represents anitrogen atom or a C—R^(2″) group and Y″ independently of X″ representsa nitrogen atom or a C—R^(9″) group, R^(1″) for each of the two R^(1″)groups independently of the other represents a radical selected from thegroup C₁-C₂₄-alkyl, C₃-C₂₀-cycloalkyl, which includes especially bothmonocyclic and also bi- and tri-cyclic cycloalkyl radicals, C₅-C₁₄-aryl,which includes especially the phenyl, naphthyl, fluorenyl radical,C₂-C₁₃-heteroaryl, wherein the number of hetero atoms, selected from thegroup N, O, S, may be from 1 to 2, wherein the two radicals R^(1″) mayalso be linked to one another,and wherein the above-mentioned radicals R^(1″) may themselves each bemono- or poly-substituted independently of one another by substituentsselected from the group hydrogen, C₁-C₂₀-alkyl, C₂-C₂O-alkenyl,C₃-C₈-cycloalkyl, C₂-C₉-hetero-alkyl, C₂-C₉-heteroaryl, wherein thenumber of hetero atoms from the group N, O, S may be from 1 to 4,C₁-C₂₀-alkoxy, hydroxy, amino of the forms NH—(C₁-C₂₀-alkyl),NH—(C₅-C₁₀-aryl), N(C₁-C₂₀-alkyl)₂, N(C₁-C₂₀-alkyl) (C₅-C₁₀-aryl),N(C₅-C₁₀-aryl)₂, N(C₁-C₂₀-alkyl/C₅-C₁₀-aryl₃)₃ ⁺, NH—CO—C₁-C₂₀-alkyl,NH—CO— carboxylato of the forms COOH and COOQ (wherein Q representseither a monovalent cation or C₁-C₈-alkyl), C₁-C₆-acyloxy, sulfinato,sulfonato of the forms SO₃H and SO₃Q′ (wherein Q′ represents either amonovalent cation, C₁-C₂₀-alkyl, or C₅-C₁₀-aryl), tri-C₁-C₆-alkylsilyl,wherein two of the mentioned substituents may also be bridged with oneanother, R^(2″)-R^(9″) represent a hydrogen, alkyl, alkenyl, cycloalkyl,aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N-(alkyl)₂,O-(aryl), NH-(aryl), N-(alkyl)(aryl), O—CO-alkyl, O—CO-aryl, F,Si(alkyl)₃, CF₃, CN, CO₂H, COH, SO₃H, CONH₂, CONH(alkyl), CON(alkyl)₂,SO₂(alkyl), SO(alkyl), SO(aryl), SO₂(aryl), SO₃(alkyl), SO₃(aryl),S-alkyl, S-aryl, NH—CO(alkyl), CO₂(alkyl), CONH₂, CO(alkyl), NHCOH,NHCO₂(alkyl), CO(aryl), CO₂(aryl) radical, wherein two or more adjacentradicals, each independently of the other (s), may also be linked to oneanother so that a condensed ring system is present and wherein in R^(2″)to R^(9″) alkyl represents a hydrocarbon radical having from 1 to 20carbon atoms which may in each case be linear or branched, alkenylrepresents a mono- or poly-unsaturated hydrocarbon radical having from 2to 20 carbon atoms which may in each case be linear or branched,cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms,aryl represents a 5- to 14-membered aromatic radical, wherein from oneto four carbon atoms in the aryl radical may also be replaced by heteroatoms from the group nitrogen, oxygen and sulfur so that a 5- to14-membered heteroaromatic radical is present, wherein the radicalsR^(2″) to R^(9″) may also carry further substituents as defined forR^(1″).

The organic phosphines and their synthesis are described inWO2004101581.

Preferred organic phosphines are selected from trisubstituted phosphinesof formula

Cpd. R^(1″) R^(5″) R^(6″) R^(3″) R^(4″) A-1 

H H H H A-2  cyclohexyl H H H H A-3  phenyl H H H H A-4  adamantyl H H HH A-5  cyclohexyl —OCH₃ H H H A-6  cyclohexyl ¹⁾ ¹⁾ H H A-7 

¹⁾ ¹⁾ H H A-8  phenyl ¹⁾ ¹⁾ H H A-9  adamantyl ¹⁾ ¹⁾ H H A-10 cyclohexylH H ²⁾ ²⁾ A-11

H H ²⁾ ²⁾ A-12 phenyl H H ²⁾ ²⁾ A-13 adamantyl H H ²⁾ ²⁾ ¹⁾ R^(5″) andR^(6″) together form a ring

²⁾ R^(3″) and R^(4″) together form a ring

Examples of preferred catalysts include the following compounds:

palladium(II) acetylacetonate, palladium(0) dibenzylidene-acetonecomplexes, palladium(II) propionate,Pd₂(dba)₃: [tris(dibenzylideneacetone) dipalladium(0)],Pd(dba)₂: [bis(dibenzylideneacetone) palladium(0)],Pd(PR₃)₂, wherein PR₃ is a trisubstituted phosphine of formula VI,Pd(OAc)₂: [palladium(II) acetate], palladium(II) chloride, palladium(II)bromide, lithium tetra-chloropalladate(II),PdCl₂(PR₃)₂; wherein PR₃ is a trisubstituted phosphine of formula VI;palladium(0) diallyl ether complexes, palladium(II) nitrate,PdCl₂(PhCN)₂: [dichlorobis(benzonitrile) palladium(II)],PdCl₂(CH₃CN): [dichlorobis(acetonitrile) palladium(II)], andPdCl₂(COD): [dichloro(1,5-cyclooctadiene) palladium(II)].

Especially preferred are PdCl₂, Pd₂(dba)₃, Pd(dba)₂, Pd(OAc)₂, orPd(PR₃)₂. Most preferred are Pd₂(dba)₃ and Pd(OAc)₂.

The palladium catalyst is present in the reaction mixture in catalyticamounts. The term “catalytic amount” refers to an amount that is clearlybelow one equivalent of the (hetero)aromatic compound(s), preferably0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on theequivalents of the (hetero)aromatic compound(s) used.

The amount of phosphines or phosphonium salts in the reaction mixture ispreferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%,based on the equivalents of the (hetero)aromatic compound(s) used. Thepreferred ratio of Pd:phosphine is 1:4.

The base can be selected from all aqueous and nonaqueous bases and canbe inorganic, or organic. It is preferable that at least 1.5 equivalentsof said base per functional boron group is present in the reactionmixture. Suitable bases are, for example, alkali and alkaline earthmetal hydroxides, carboxylates, carbonates, fluorides and phosphatessuch as sodium and potassium hydroxide, acetate, carbonate, fluoride andphosphate or also metal alcoholates. It is also possible to use amixture of bases. The base is preferably a lithium salt, such as, forexample, lithium alkoxides (such as, for example, lithium methoxide andlithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluorideand/or phosphate.

The at present most preferred base is aqueous LiOHxH2O (monohydrate ofLiOH) and (waterfree) LiOH.

The reaction is typically conducted at about 0° C. to 180° C.,preferably from 20 to 160° C., more preferably from 40 to 140° C. andmost preferably from 40 to 120° C. A polymerization reaction may take0.1, especially 0.2 to 100 hours.

In a preferred embodiment of the present invention the solvent is THF,the base is Li—OH*H₂O and the reaction is conducted at refluxtemperature of THF (about 65° C.).

The solvent is for example selected from toluene, xylenes, anisole, THF,2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene orsolvent mixtures comprising one or more solvents like e.g. THF/tolueneand optionally water. Most preferred is THF, or THF/water.

Advantageously, the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃,(tris(dibenzylideneacetone)dipalladium(0)) and an organic phosphine A-1to A-13,

b) LiOH, or LiOHxH2O; and

c) THF, and optionally water. If the monohydrate of LiOH is used, nowater needs to be added.

Most preferred the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃(tris(dibenzylideneacetone)dipalladium(0)) and

b) LiPHxH₂O; and

c) THF. The palladium catalyst is present in an amount of preferablyabout 0.5 mol-%, based on the equivalents of the (hetero)aromaticcompound(s) used. The amount of phosphines or phosphonium salts in thereaction mixture is preferably about 2 mol-%, based on the equivalentsof the (hetero)aromatic compound(s) used. The preferred ratio ofPd:phosphine is about 1:4.

Preferably the polymerization reaction is conducted under inertconditions in the absence of oxygen. Nitrogen and more preferably argonare used as inert gases.

The process described in WO2010/136352 is suitable for large-scaleapplications, is readily accessible and convert starting materials tothe respective polymers in high yield, with high purity and highselectivity. The process can provide polymers having weight averagemolecular weights of at least 10,000, more preferably at least 20,000,most preferably at least 30,000. The at present most preferred polymershave a weight average molecular weight of 30,000 to 80,000 Daltons.Molecular weights are determined according to high-temperature gelpermeation chromatography (HT-GPC) using polystyrene standards. Thepolymers preferably have a polydispersibility of 1.01 to 10, morepreferably 1.1 to 3.0, most preferred 1.5 to 2.5.

If desired, a monofunctional aryl halide or aryl boronate, such as, forexample,

(X² is Br, I, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K) may be used as a chain-terminator in such reactions,which will result in the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

The polymers of the present invention can also be sythesized by theStille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004,14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). Toprepare polymers corresponding to formula VII a dihalogenide of formulaX¹⁰-A-X¹⁰ is reacted with a compound of formula X^(11′)—COM¹-X^(11′), ora dihalogenide of formula X¹⁰—COM¹-X¹⁰ is reacted with a compound offormula X^(11′)-A-X^(11′), wherein X^(11′) is a group —SnR²⁰⁷R²⁰⁸R²⁰⁹and X¹⁰ is as defined above, in an inert solvent at a temperature inrange from 0° C. to 200° C. in the presence of a palladium-containingcatalyst, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and areH or C₁-C₆alkyl, wherein two radicals optionally form a common ring andthese radicals are optionally branched or unbranched. It must be ensuredhere that the totality of all monomers used has a highly balanced ratioof organotin functions to halogen functions. In addition, it may proveadvantageous to remove any excess reactive groups at the end of thereaction by end-capping with monofunctional reagents. In order to carryout the process, the tin compounds and the halogen compounds arepreferably introduced into one or more inert organic solvents andstirred at a temperature of from 0 to 200° C., preferably from 30 to170° C. for a period of from 1 hour to 200 hours, preferably from 5hours to 150 hours. The crude product can be purified by methods knownto the person skilled in the art and appropriate for the respectivepolymer, for example repeated re-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example,ethers, for example diethyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl etherand tert-butyl methyl ether, hydrocarbons, for example hexane,isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols,for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol,1-butanol, 2-butanol and tert-butanol, ketones, for example acetone,ethyl methyl ketone and isobutyl methyl ketone, amides, for exampledimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,nitriles, for example acetonitrile, propionitrile and butyronitrile, andmixtures thereof.

The palladium and phosphine components should be selected analogously tothe description for the Suzuki variant.

Alternatively, the polymers of the present invention can also besynthesized by the Negishi reaction using a zinc reagent A-(ZnX¹²)₂,wherein X¹² is halogen and halides, and COM¹-(X²³)₂, wherein X²³ ishalogen or triflate, or using A-(X²³)₂ and COM¹-(ZnX²³)₂. Reference is,for example, made to E. Negishi et al., Heterocycles 18 (1982) 117-22.

Alternatively, the polymers of the present invention can also besynthesized by the Hiyama reaction using a organosilicon reagentA-(SiR²¹⁰R²¹¹R²¹²)₂, wherein R²¹⁰, R²¹¹ and R²¹² are identical ordifferent and are halogen, or C₁-C₆alkyl, and COM¹-(X²³)₂, wherein X²³is halogen or triflate, or using A-(X²³)₂ and COM¹-(SiR²¹⁰R²¹¹R²¹²)₂.Reference is, for example, made to T. Hiyama et al., Pure Appl. Chem. 66(1994) 1471-1478 and T. Hiyama et al., Synlett (1991) 845-853.

Homopolymers of the type (A)_(n) can be obtained via Yamamoto couplingof dihalides X¹⁰-A-X¹⁰, where X¹⁰ is halogen, preferably bromide.Alternatively homopolymers of the type (A)_(n) can be obtained viaoxidative polymerization of units X¹⁰-A-X¹⁰, where X¹⁰ is hydrogen, e.g.with FeCl₃ as oxidizing agent.

The compounds of the formula

X²Ar³_(c)Ar²_(b)Ar¹_(a)YAr^(1′)_(a′)Ar^(2′)_(b′)Ar^(3′)_(c′)X^(2′) (V) are intermediatesin the production of the polymers of the present invention, are new andform a further subject of the present invention. a, a′, b, b′, c, c′, Y,Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are as defined above, and X²and X^(2′) are independently of each other halogen, especially Br, or J,ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical ordifferent and are H or C₁-C₈alkyl, wherein two radicals optionally forma common ring and these radicals are optionally branched or unbranchedand X¹² is a halogen atom, very especially I, or Br; or —OS(O)₂CF₃,—OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—,wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² areindependently of each other hydrogen, or a C₁-C₁₀alkyl group, especially—C(CH₃)₂C(CH₃)₂—, —C(CH₃)₂CH₂C(CH₃)₂—, or —CH₂C(CH₃)₂CH₂—, and Y¹³ andY¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group. X²and X^(2′) are preferably the same.

Y is preferably a group of formula

more preferably a group of formula

U¹ and U² are preferably O, more preferably NR¹. T¹ and T² arepreferably hydrogen. Examples of compounds of formula V are shown below:

wherein X² is as defined above,

U¹ is O, or NR¹; U² is O, or NR²;

T¹ and T² are independently of each other hydrogen, or C₁-C₂₅alkyl,especially hydrogen;R¹ and R² may be the same or different and are selected from aC₁-C₃₈alkyl group, especially C₈-C₃₆alkyl group;R³ and R^(3′) are independently of each other hydrogen or C₁-C₂₅alkyl;andR⁸ and R^(8′) are independently of each other hydrogen or C₁-C₂₅alkyl,especially C₁-C₂₅alkyl.

Among the compounds of formula V the following compounds are preferred:

The polymers, wherein R¹ and/or R² are hydrogen can be obtained by usinga protecting group which can be removed after polymerization. Referenceis made, for example, to EP-A-0648770, EP-A-0648817, EP-A-0742255,EP-A-0761772, WO98/32802, WO98/45757, WO98/58027, WO99/01511,WO00/17275, WO00/39221, WO00/63297 and EP-A-1086984, which describe thebasic procedural method. Conversion of the pigment precursor into itspigmentary form is carried out by means of fragmentation under knownconditions, for example thermally, optionally in the presence of anadditional catalyst, for example the catalysts described in WO00/36210.

An example of such a protecting group is group of formula

wherein L is any desired group suitable for imparting solubility.

L is preferably a group of formula

wherein Z¹, Z² and Z³ are independently of each other C₁-C₆alkyl,Z⁴ and Z⁸ are independently of each other C₁-C₆alkyl, C₁-C₆alkylinterrupted by oxygen, sulfur or N(Z¹²)₂, or unsubstituted orC₁-C₆alkyl-, C₁-C₆alkoxy-, halo-, cyano- or nitro-substituted phenyl orbiphenyl,Z⁶, Z⁶ and Z⁷ are independently of each other hydrogen or C₁-C₆alkyl,Z⁹ is hydrogen, C₁-C₈alkyl or a group of formula

Z¹⁰ and Z¹¹ are each independently of the other hydrogen, C₁-C₆alkyl,C₁-C₆alkoxy, halogen, cyano, nitro, N(Z¹²)₂, or unsubstituted or halo-,cyano-, nitro-, C₁-C₆alkyl- or C₁-C₆alkoxy-substituted phenyl,Z¹² and Z¹³ are C₁-C₆alkyl, Z¹⁴ is hydrogen or C₁-C₆alkyl, and Z¹⁵ ishydrogen, C₁-C₆alkyl, or unsubstituted or C₁-C₆alkyl-substituted phenyl,Q* is p,q-C₂-C₆alkylene unsubstituted or mono- or poly-substituted byC₁-C₆alkoxy, C₁-C₆alkylthio or C₂-C₁₂dialkylamino, wherein p and q aredifferent position numbers,X″ is a hetero atom selected from the group consisting of nitrogen,oxygen and sulfur, m′ being the number 0 when X″ is oxygen or sulfur andm being the number 1 when X″ is nitrogen, andL¹ and L² are independently of each other unsubstituted or mono- orpoly-C₁-C₁₂alkoxy-, —C₁-C₁₂alkylthio-, —C₂-C₂₄dialkylamino-,—C₆-C₁₂aryloxy-, —C₆-C₁₂arylthio-, —C₇-C₂₄alkylarylamino- or—C₁₂-C₂₄diarylamino-substituted C₁-C₆alkyl or[-(p′,q′-C₂-C₆alkylene)-Z—]_(n′)—C₁-C₆alkyl, n′ being a number from 1 to1000, p′ and q′ being different position numbers, each Z independentlyof any others being a hetero atom oxygen, sulfur orC₁-C₁₂alkyl-substituted nitrogen, and it being possible forC₂-C₆alkylene in the repeating [—C₂-C₆alkylene-Z—] units to be the sameor different,and L₁ and L₂ may be saturated or unsaturated from one to ten times, maybe uninterrupted or interrupted at any location by from 1 to 10 groupsselected from the group consisting of —(C═O)— and —C₆H₄—, and may carryno further substituents or from 1 to 10 further substituents selectedfrom the group consisting of halogen, cyano and nitro. Most preferred Lis a group of formula

The synthesis of the compounds of formula H-A-H can be done in analogyto the methods described in C. Greenhalgh et al., Dyes and Pigments 1(1980) 103-120 and G Hallas et al. Dyes and Pigments 48 (2001) 121-132.

In the context of the present invention, the terms halogen, C₁-C₂₅alkyl(C₁-C₁₈alkyl), C₂-C₂₅alkenyl (C₂-C₁₈alkenyl), C₂₋₂₅ alkynyl (C₂₋₁₈alkynyl), aliphatic groups, aliphatic hydrocarbon groups, alkylene,alkenylene, cycloaliphatic hydrocarbon groups, cycloalkyl, cycloalkenylgroups, C₁-C₂₅alkoxy (C₁-C₁₈alkoxy), C₁-C₁₈perfluoroalkyl, carbamoylgroups, C₆-C₂₄aryl (C₆-C₁₈aryl), C₇-C₂₅aralkyl and heteroaryl are eachdefined as follows unless stated otherwise:

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, wherepossible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl.

C₂-C₂₅alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branchedalkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₅ alkynyl (C₂₋₁₈ alkynyl) is straight-chain or branched andpreferably C₂₋₈ alkynyl, which may be unsubstituted or substituted, suchas, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CHs. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

An aliphatic hydrocarbon group having up to 25 carbon atoms is a linearor branched alkyl, alkenyl or alkynyl (also spelled alkinyl) grouphaving up to 25 carbon atoms as exemplified above.

Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) freevalencies, e.g. trimethylene or tetramethylene.

Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one)free valencies, e.g. —CH₂—CH═CH—CH₂—.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CHs. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl groupwhich may be substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups.

A cycloaliphatic-aliphatic group is an aliphatic group substituted by acycloaliphatic group, wherein the terms “cycloaliphatic” and “aliphatic”have the meanings given herein and wherein the free valency extends fromthe aliphatic moiety. Hence, a cycloaliphatic-aliphatic group is forexample a cycloalkyl-alkyl group.

A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkylgroup, e.g. cyclohexyl-methyl.

A “cycloalkenyl group” means an unsaturated alicyclic hydrocarbon groupcontaining one or more double bonds, such as cyclopentenyl,cyclopentadienyl, cyclohexenyl and the like, which may be unsubstitutedor substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups and/or condensed with phenyl groups.

For example, a cycloalkyl or cycloalkenyl group, in particular acyclohexyl group, can be condensed one or two times with phenyl whichcan be substituted one to three times with C₁-C₄-alkyl. Examples of suchcondensed cyclohexyl groups are groups of the formulae:

in particular

which can be substituted in the phenyl moieties one to three times withC₁-C₄-alkyl.

A bivalent group of the formula XIl wherein R²⁸ and R²⁷ togetherrepresent alkylene or alkenylene which may be both bonded via oxygenand/or sulfur to the thienyl residue and which may both have up to 25carbon atoms, is e.g. a group of the formula

wherein A represents linear or branched alkylene having up to 25 carbonatoms, preferably ethylene or propylene which may be substituted by oneor more alkyl groups, and Y represents oxygen or sulphur. For example,the bivalent group of the formula —Y-A-O— represents —O—CH₂—CH₂—O— or—O—CH₂—CH₂—CH₂—O—.

A group of the formula XI wherein two groups R²² to R²⁶ which are in theneighborhood of each other, together represent alkylene or alkenylenehaving up to 8 carbon atoms, thereby forming a ring, is e.g. a group ofthe formula

wherein in the group of the formula XXXII R²³ and R²⁴ together represent1,4-butylene and in the group of the formula XXXIII R²³ and R²⁴ togetherrepresent 1,4-but-2-en-ylene.

C₁-C₂₅alkoxy groups (C₁-C₁₈alkoxy groups) are straight-chain or branchedalkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy,octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy andoctadecyloxy. Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy,2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy,n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferablyC₁-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthiogroup” means the same groups as the alkoxy groups, except that theoxygen atom of the ether linkage is replaced by a sulfur atom.

C₁-C₁₈perfluoroalkyl, especially C₁-C₄perfluoroalkyl, is a branched orunbranched radical such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃,—CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)_(3.)

The term “carbamoyl group” is typically a C₁₋₁₈carbamoyl radical,preferably C₁₋₈carbamoyl radical, which may be unsubstituted orsubstituted, such as, for example, carbamoyl, methylcarbamoyl,ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

A cycloalkyl group is typically C₃-C₁₂cycloalkyl, such as, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl,cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted orsubstituted. The cycloalkyl group, in particular a cyclohexyl group, canbe condensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen and cyano. Examples of suchcondensed cyclohexyl groups are:

in particular

wherein R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵ and R¹⁵⁶ are independently of eachother C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particularhydrogen.

C₆-C₂₄aryl (C₆-C₁₈aryl) is typically phenyl, indenyl, azulenyl,naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthylenyl,fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl,naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, oranthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl,9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may beunsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl,1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or9-phenanthryl, which may be unsubstituted or substituted.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl,α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl,ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl orω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, andparticularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl,β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, orω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbongroup and aromatic hydrocarbon group may be unsubstituted orsubstituted. Preferred examples are benzyl, 2-phenylethyl,3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

Heteroaryl is typically C₂-C₂₀heteroaryl, i.e. a ring with five to sevenring atoms or a condensed ring system, wherein nitrogen, oxygen orsulfur are the possible hetero atoms, and is typically an unsaturatedheterocyclic group with five to 30 atoms having at least six conjugatedic-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl,thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl,pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl,chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl,carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl,isoxazolyl, thienothienyl, furazanyl or phenoxazinyl, which can beunsubstituted or substituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, a carbamoyl group, a nitro group or asilyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylthio,halogen, halo-C₁-C₈alkyl, or a cyano group.

C₁-C₁₀alkyl interrupted by one or more O is, for example,(CH₂CH₂O)₁₋₉—R^(x), where R^(x) is H or C₁-C₁₀alkyl,CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₁₀alkyl, and R^(y′)embraces the same definitions as R^(y) or is H.

If a substituent, such as, for example R³, occurs more than one time ina group, it can be different in each occurrence.

A mixture containing a polymer of the present invention results in asemi-conducting layer comprising a polymer of the present invention(typically 5% to 99.9999% by weight, especially 20 to 85% by weight) andat least another material. The other material can be, but is notrestricted to a fraction of the same polymer of the present inventionwith different molecular weight, another polymer of the presentinvention, a semi-conducting polymer, organic small molecules, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), insulator materials like the ones described for the gatedielectric (PET, PS etc.).

The polymers of the present invention can be blended with compounds offormula III according to the present invention, or small moleculesdescribed, for example, in WO2009/047104, WO2010108873(PCT/EP2010/053655), WO09/047104, U.S. Pat. No. 6,690,029, WO2007082584,and WO2008107089:

WO2007082584:

WO2008107089:

wherein one of Y^(1′) and Y^(2′) denotes —CH═ or ═CH— and the otherdenotes —X*—,one of Y^(3′) and Y^(4′) denotes —CH═ or ═CH— and the other denotes—X*—,

X* is —O—, —S—, —Se— or —NR′″—,

R* is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20C-atoms, or aryl having 2-30 C-atoms, all of which are optionallyfluorinated or perfluorinated,R′ is H, F, Cl, Br, I, CN, straight-chain or branched alkyl or alkoxyhaving 1 to 20 C-atoms and optionally being fluorinated orperfluorinated, optionally fluorinated or perfluorinated aryl having 6to 30 C-atoms, or CO₂R″, with R″ being H, optionally fluorinated alkylhaving 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30C-atoms,R′″ is H or cyclic, straight-chain or branched alkyl with 1 to 10C-atoms, y is 0, or 1, x is 0, or 1

The polymer can contain a small molecule, or a mixture of two, or moresmall molecule compounds.

Accordingly, the present invention also relates to an organicsemiconductor material, layer or component, comprising a polymeraccording to the present invention.

The polymers of the invention can be used as the semiconductor layer insemiconductor devices. Accordingly, the present invention also relatesto semiconductor devices, comprising a polymer of the present invention,or an organic semiconductor material, layer or component. Thesemiconductor device is especially an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor.

The polymers of the invention can be used alone or in combination as theorganic semiconductor layer of the semiconductor device. The layer canbe provided by any useful means, such as, for example, vapor deposition(for materials with relatively low molecular weight) and printingtechniques. The compounds of the invention may be sufficiently solublein organic solvents and can be solution deposited and patterned (forexample, by spin coating, dip coating, slot die coating, ink jetprinting, gravure printing, flexo printing, offset printing, screenprinting, microcontact (wave)-printing, drop or zone casting, or otherknown techniques).

The polymers of the invention can be used in integrated circuitscomprising a plurality of OTFTs, as well as in various electronicarticles. Such articles include, for example, radio-frequencyidentification (RFID) tags, backplanes for flexible displays (for usein, for example, personal computers, cell phones, or handheld devices),smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-,mechanical- or temperature sensors), especially photodiodes, or securitydevices and the like.

A further aspect of the present invention is an organic semiconductormaterial, layer or component comprising one or more polymers, orcompounds of the present invention. A further aspect is the use of thepolymers or materials of the present invention in an organicphotovoltaic (PV) device (solar cell), a photodiode, or an organic fieldeffect transistor (OFET). A further aspect is an organic photovoltaic(PV) device (solar cell), a photodiode, or an organic field effecttransistor (OFET) comprising a polymer or material of the presentinvention.

The polymers of the present invention are typically used as organicsemiconductors in form of thin organic layers or films, preferably lessthan 30 microns thick. Typically the semiconducting layer of the presentinvention is at most 1 micron (=1 μm) thick, although it may be thickerif required. For various electronic device applications, the thicknessmay also be less than about 1 micron thick. For example, for use in anOFET the layer thickness may typically be 100 nm or less. The exactthickness of the layer will depend, for example, upon the requirementsof the electronic device in which the layer is used.

For example, the active semiconductor channel between the drain andsource in an OFET may comprise a layer of the present invention.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,    -   a drain electrode,    -   a gate electrode,    -   a semiconducting layer,    -   one or more gate insulator layers, and    -   optionally a substrate, wherein the semiconductor layer        comprises one or more polymers of the present invention.

The gate, source and drain electrodes and the insulating andsemiconducting layer in the OFET device may be arranged in any sequence,provided that the source and drain electrode are separated from the gateelectrode by the insulating layer, the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and asecond side, a gate electrode located on the first side of theinsulator, a layer comprising a polymer of the present invention locatedon the second side of the insulator, and a drain electrode and a sourceelectrode located on the polymer layer.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and manufacturing methods of an OFET device areknown to the person skilled in the art and are described in theliterature, for example in WO03/052841.

The gate insulator layer may comprise for example a fluoropolymer, likee.g. the commercially available Cytop 809M®, or Cytop 107M® (from AsahiGlass). Preferably the gate insulator layer is deposited, e.g. byspin-coating, doctor blading, wire bar coating, spray or dip coating orother known methods, from a formulation comprising an insulator materialand one or more solvents with one or more fluoro atoms (fluorosolvents),preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC25®(available from Acros, catalogue number 12380). Other suitablefluoropolymers and fluorosolvents are known in prior art, like forexample the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), orFluoro-pel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No.12377).

The semiconducting layer comprising a polymer of the present inventionmay additionally comprise at least another material. The other materialcan be, but is not restricted to another polymer of the presentinvention, a semi-conducting polymer, a polymeric binder, organic smallmolecules different from a polymer of the present invention, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), and insulator materials like the ones described for thegate dielectric (PET, PS etc.). As stated above, the semiconductivelayer can also be composed of a mixture of one or more polymers of thepresent invention and a polymeric binder. The ratio of the polymers ofthe present invention to the polymeric binder can vary from 5 to 95percent. Preferably, the polymeric binder is a semicristalline polymersuch as polystyrene (PS), high-density polyethylene (HDPE),polypropylene (PP) and polymethylmethacrylate (PMMA). With thistechnique, a degradation of the electrical performance can be avoided(cf. WO2008/001123A1).

The polymers of the present invention are advantageously used in organicphotovoltaic (PV) devices (solar cells). Accordingly, the inventionprovides PV devices comprising a polymer according to the presentinvention. A device of this construction will also have rectifyingproperties so may also be termed a photodiode. Photoresponsive deviceshave application as solar cells which generate electricity from lightand as photodetectors which measure or detect light.

The PV device comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) an anode (electrode),(f) a substrate.

The photoactive layer comprises the polymers of the present invention.Preferably, the photoactive layer is made of a conjugated polymer of thepresent invention, as an electron donor and an acceptor material, like afullerene, particularly a functionalized fullerene PCBM, as an electronacceptor. As stated above, the photoactive layer may also contain apolymeric binder. The ratio of the polymers of formula I to thepolymeric binder can vary from 5 to 95 percent. Preferably, thepolymeric binder is a semicristalline polymer such as polystyrene (PS),high-density polyethylene (HDPE), polypropylene (PP) andpolymethylmethacrylate (PMMA).

For heterojunction solar cells the active layer comprises preferably amixture of a polymer of the present invention and a fullerene, such as[60]PCBM (=6,6-phenyl-C₆₁-butyric acid methyl ester), or [70]PCBM, in aweight ratio of 1:1 to 1:3. The fullerenes useful in this invention mayhave a broad range of sizes (number of carbon atoms per molecule). Theterm fullerene as used herein includes various cage-like molecules ofpure carbon, including Buckminsterfullerene (C₆₀) and the related“spherical” fullerenes as well as carbon nanotubes. Fullerenes may beselected from those known in the art ranging from, for example,C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₉to C₉₆. Most preferably the fullerene is C₆₀ or C₇₀, such as [60]PCBM,or [70]PCBM. It is also permissible to utilize chemically modifiedfullerenes, provided that the modified fullerene retains acceptor-typeand electron mobility characteristics. The acceptor material can also bea material selected from the group consisting of any semi-conductingpolymer, such as, for example, a polymer of the present invention,provided that the polymers retain acceptor-type and electron mobilitycharacteristics, organic small molecules, carbon nanotubes, inorganicparticles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a polymer of the present invention asan electron donor and a fullerene, particularly functionalized fullerenePCBM, as an electron acceptor. These two components are mixed with asolvent and applied as a solution onto the smoothing layer by, forexample, the spin-coating method, the drop casting method, theLangmuir-Blodgett (“LB”) method, the ink jet printing method and thedripping method. A squeegee or printing method could also be used tocoat larger surfaces with such a photoactive layer. Instead of toluene,which is typical, a dispersion agent such as chlorobenzene is preferablyused as a solvent. Among these methods, the vacuum deposition method,the spin-coating method, the ink jet printing method and the castingmethod are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)(f) optionally an extra electrode to match the energy level,(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(h) a photoactive layer,(i) optionally a smoothing layer,(j) an anode (electrode),(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or filmscomprising the polymers of the present invention can also be used aloneor together with other materials in or as alignment layers in LCD orOLED devices, as described for example in US2003/0021913.

It is another object of the present invention to provide compounds,which show high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability, whenused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes.

In a further embodiment the present invention relates to compounds ofthe formula

A¹-YA³-Y¹⁵_(o)A⁴-Y¹⁶_(p)A⁵-Y¹⁷_(q)A² (III), wherein Y, Y¹⁵, Y¹⁶and Y¹⁷ are independently of each other a group of formula

o is 0, or 1, p is 0, or 1, q is 0, or 1;A¹ and A² are independently of each other a group of formulaAr¹_(a)Ar²_(b)Ar³_(c)—R¹⁰,A³, A⁴ and A⁵ are independently of each other a group of formula*Ar⁴_(k)Ar⁵_(l)Ar⁶_(r)Ar⁷_(z)*,k is 1, 2, or 3; l is 0, 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2,or 3;R¹⁰ is hydrogen, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which issubstituted one or more times by E and/or interrupted one or more timesby D,

COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, whichis substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈thioalkoxy,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interruptedby D, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G, or agroup of formulae IVa to IVm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ represent independently of each otherH, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by Eand/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, aC₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substitutedby G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, orC₇-C₂₅aralkyl, which is substituted by G,R²⁷ and R²⁸ are independently of each other hydrogen, C₁-C₂₅alkyl,halogen, cyano or C₇-C₂₅aralkyl, or R²⁷ and R²⁸ together representalkylene or alkenylene which may be both bonded via oxygen and/or sulfurto the thienyl residue and which may both have up to 25 carbon atoms,R⁵⁹ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which may optionally be interrupted by one or more oxygen or sulphuratoms; or C₇-C₂₅arylalkyl,

D is —CO—, —COO—, —S—, —O—, or NR¹¹²—,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, orhalogen,G is E, or C₁-C₁₈alkyl, andR¹¹² and R¹¹³ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—;R²¹⁴ and R²¹⁵ are independently of each other hydrogen, C₁-C₁₈alkyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR²¹⁶;R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl orC₂-C₂₀heteroaryl;Ar⁴, Ar⁵, Ar⁶ and Ar⁷ have independently of each other the meaning ofAr¹, or are independently of each other a group of formula XVa, XVb,XVc, XVd, XVe, XVf, or XVg, XVI, or XVII (as defined in claim 1), and a,b, c, Ar¹, Ar², Ar³, T¹, T², U¹ and U² are as defined above.

Y is preferably a group of formula

more preferably a group of formula

U¹ and U² are preferably O, more preferably NR¹. T¹ and T² arepreferably hydrogen.

Among the compounds of the formula III compounds of formula

are more preferred, whereinA¹, A², A³, A⁴, A⁵, T¹, T², U¹ and U² are as defined above,T^(1′), T^(2′), T^(1″), T^(2″), T^(1″) and T^(2″) independently of eachother have the meaning of T¹, andU^(1′), U^(2′), U^(1″), U^(2″), U^(1″) and U^(2″) independently of eachother have the meaning of U¹.

More preferred are compounds of the formula IIIa, IIIb and IIIc, evenmore preferred are compounds of the formula IIIa and IIIb, and mostpreferred are compounds of the formula IIIa.

Compounds of the formula R¹⁰Ar¹_(a) YAr^(1′)_(a′)R^(10′) (III′) aremore preferred, wherein Y is a group of formula

especially

U¹ is O, S, or NR¹; U² is O, S, or NR²;

a is 1, 2, or 3, a′ is 1, 2, or 3; wherein R^(10′) has the meaning ofR¹⁰, R¹⁰, T¹, T², R¹, R², Ar¹ and Ar^(1′) are as defined above.

For R^(10′) the same preferences apply as for R¹⁰. For T¹, T², R¹, R²,Ar¹ and Ar^(1′) the same preferences apply as in case of the polymersaccording to the present invention.

In said embodiment Y is preferably a group of formula

U¹ and U² may be different, but are preferably the same. U¹ ispreferably O or NR¹; more preferably NR¹. U² is preferably O or NR¹;more preferably NR¹.

T¹ and T² may be different, but are preferably the same. T¹ and T² arepreferably independently of each other hydrogen, halogen, cyano,—COOR¹⁰³, —OCOR¹⁰³, —OR¹⁰³, —SR¹⁰³, C₁-C₂₅alkyl, which may besubstituted by E and/or interrupted by D; more preferably hydrogen,halogen, cyano, —OR¹⁰³, or C₁-C₂₅alkyl; most preferred hydrogen, orC₁-C₂₅alkyl, especially hydrogen.

R¹ and R² may be different, but are preferably the same. More preferablyR¹ and R² are selected from hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl,C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl,C₅-C₁₂cycloalkyl, phenyl, or naphthyl which can optionally besubstituted one or more times with C₁-C₁₂alkyl or C₁-C₁₂alkoxy,—CO—C₅-C₁₂cycloalkyl and —COO—C₁-C₁₈alkyl. More preferably R¹ and R² areC₁-C₅₀alkyl group. Most preferred R¹ and R² are a C₁-C₃₈alkyl group.

a and a′ may be different, but are preferably the same. a is 1, 2, or 3,a′ is 1, 2, or 3.

Ar¹ and Ar^(1′) may be different, but are preferably the same.Preferably, Ar¹ and Ar^(1′) are independently of each a group of formulaXIa, XIb, XIc, XIe, XIf, XIl, XIp, XIr, XIs, XIx, XIIf, XIIg, XIIIa,XIIId, or XIIIl. More preferably, Ar¹ and Ar^(1′) are a group of formulaXIa, XIb, XIe, XIf, XIr, XIx, or XIIIa. Still more preferably Ar¹ andAr^(1′) are a group of formula XIa, XIb, or XIf. Most preferred Ar¹ andAr^(1′) are a group of formula XIa, or XIf, especially XIa.

Among the compounds of formula IIIa compounds of formula

are more preferred, wherein R¹⁰ and R^(10′) are as defined above,U¹ is O, or NR¹, preferably NR¹; U² is O, or NR², preferably NR²;T¹ and T² are independently of each other hydrogen, or C₁-C₂₅alkyl,especially hydrogen;R¹ and R² may be the same or different and are selected from aC₁-C₃₈alkyl group, especially a C₈-C₃₆alkyl group;R³ and R^(3′) are independently of each other hydrogen, halogen, cyanoor C₁-C₂₅alkyl, especially hydrogen or C₁-C₂₅alkyl; andR⁸ and R^(8′) are independently of each other hydrogen or C₁-C₂₅alkyl,especially C₁-C₂₅alkyl.

In said embodiment compounds of the formula (IIIa), (IIIb), (IIIc),(IIId), (IIIf), (IIIg), (IIIh) and (IIIm) are even more preferred.

Examples of specific compounds are shown below:

In another preferred embodiment the present invention is directed tocompounds of formula

whereinA¹ and A² are independently of each other a group of formula

A³ is a group of formula

andU¹, U², U^(1′) and U^(2′) independently of each other NR¹, wherein R¹ isa C₁-C₃₈alkyl group, especially a C₈-C₃₆alkyl group.

Examples of compounds of formula IIIb are shown below:

A process for the preparation of a compound of formula

comprises reacting one to three, preferably two equivalents of aketoamide of formula

with one equivalent of a 1,4-cyclohexanedion of the formula

especially

in the presence of a base, such as, for example, such as, for example,NaH, NaOH, KOH, an amine, such as, for example, triethylamine; Na₂CO₃,K₂CO₃, butyllithium, sodium methoxide, sodium ethoxide, especially NaH,NaOH, KOH, sodium methoxide or sodium ethoxide; in a suitable solvent,such as, for example, tetrahydrofurane, dimethylformamide, ethanol,methanol, isopropanol, dimethylacetamide, dioxane, especiallytetrahydrofurane, methanol, ethanol, or isopropanol; to get anintermediate product of the formula

which is then treated with an acid, such as, for example, sulfuric acid,to get a compound of formula (IIIa′), wherein R¹, R², T¹, T², and A¹ areas defined above. The intermediate product of the formula (IX), whichmight spontaneously dehydrate, or cyclize during the reaction, or workup to a mixture containing at least one of the following compounds (IX)to (IXg):

The first reaction step can be done preferably under a nitrogenatmosphere in a temperature range from −50 to 100° C., preferably from−30 to 100° C. and more preferably from −30 to 60° C. in a time rangefrom 0.1 to 24 hours, preferably from 1 to 12 hours. The amount of thebase used can be catalytically or in the range of one to fourequivalents calculated on the equivalents of the 1,4-cyclohexanedione,preferably 1.5 to 2.5 equivalents, more preferably 2 to 2.5 equivalents.The work up can be done by quenching the reaction by the addition ofwater, or by the addition of water containing an acid, such as, forexample, acetic acid, or ammoniumhydrochloride. The reaction mixture isthen extracted by a suitable solvent, such as, for example, ethylacetate, diethylether, methylene chloride, chloroform, toluene, orbutylacetate.

In the second reaction step the intermediate mixture obtained in thefirst step is treated with an acid, such as, for example, sulfuric acid,methanesulfonic acid, trifluoromethanesulfonic acid,p-toluenesulfonicacid, acetic acid, trifluoroacetic acid, phosphoricacid, HCl, HBr, HF, HI, or by the addition of thionyl chloride,especially with sulfuric acid, HCl or trifluoroacetic acid together witha suitable solvent, such as, for example, methylene chloride,chloroform, ethylacetate, water or just the neat acid to get a compoundof formula (IIIa′). The second reaction step is preferably done in atemperature range from −20° C. to 100° C., more preferably from 0° C. to80° C., most preferred from 20° C. to 40° C.; in a time range from 0.1to 24 hours, preferably from 1 to 12 hours. Additional solvents, suchas, for example, ethyl acetate, toluene, diethyl ether, methylenechloride, chloroform, chlorobenzene, xylene, or butyl acetate; can beadded for work up. Advantage reaction conditions are described in theExamples that follow.

Compounds of formula

are side products in the process for the preparation of compounds offormula IIIa′.

Compounds of formula

can be prepared according to the above described process for compoundsof formula (IIIa′) by using instead of the 1,4-cyclohexanedione of theformula

a 1,2-cyclohexanedione of the formula

especially

After the first step an intermediate of formula

is obtained (including similar derivatives by dehydration andcyclization as shown above in case of the compound of formula (IX))which in a second step on treatment with an acid results in the compoundof formula (VIII). The process also includes two reaction steps. Thefirst step is done under basic conditions, the second step is done underacidic conditions.

Reference is made to WO2009/047104 and PCT/EP2012/061777 with respect tothe preparation of the compounds of formula III.

In addition, the present invention is directed to a process for thepreparation of a compound of formula (IIIa′), wherein a1,4-cyclohexanedion of the formula

is used as starting material.

Compounds of the formula

(U¹═U^(1′)═U²═U^(2′)═NR¹, A³ is a group of formula*Ar⁴_(k)Ar⁵_(l)Ar⁶_(r)Ar⁷_(z)*, Ar⁴ is Ar⁷, k is 1, or 2, z is1, or 2) may be prepared by reacting a compound of formula

with a compound of formula X^(16′)Ar⁵_(l)Ar⁶_(r)X^(16′), whereinX^(16′) is —B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

and X¹⁶ is halogen, such as, for example, Br, or I.

The Suzuki reaction is typically conducted at about 0° C. to 180° C. inan aromatic hydrocarbon solvent such as toluene, xylene. Other solventssuch as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofurancan also be used alone, or in mixtures with an aromatic hydrocarbon. Anaqueous base, preferably sodium carbonate or bicarbonate, potassiumphosphate, potassium carbonate or bicarbonate is used as activationagent for the boronic acid, boronate and as the HBr scavenger. Acondensation reaction may take 0.2 to 100 hours. Organic bases, such as,for example, tetraalkylammonium hydroxide, and phase transfer catalysts,such as, for example TBAB, can promote the activity of the boron (see,for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003)1407 and references cited therein). Other variations of reactionconditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59(1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol.Rapid Commun. 17 (1996) 239-252.

In the above Suzuki coupling reactions the halogen X¹⁶ on thehalogenated reaction partner can be replaced with the X^(16′) moiety andat the same time the X^(16′) moiety of the other reaction partner isreplaced by X¹⁶.

In an additional embodiment the present invention is directed tocompounds of formula

A^(1″)—Y-A³-Y¹⁵A⁴-Y¹⁶_(p)A⁵-Y¹⁷_(q)A^(2″) (XX), whereinA^(1″) and A^(2″) are independently of each other a group of formulaAr¹_(a)Ar²_(b)Ar³]_(c)—X³,X³ is independently in each occurrence halogen, very especially I, orBr; ZnX¹², —SnR²⁰⁷R²⁰⁹R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical ordifferent and are H or C₆alkyl, wherein two radicals optionally form acommon ring and these radicals are optionally branched or unbranched andX¹² is a halogen atom, very especially I, or Br; —OS(O)₂CF₃,—OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₂alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₂alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,—CH₂C(CH₃)₂CH₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₂alkyl group; a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵,Y¹⁶, Y¹⁷, A³, A⁴ and A⁵ are as defined above.

The compound of formula (XX) is preferably a compound of formulaA^(1″)—Y-A³-Y¹⁵-A^(2″) (XXa). The compounds of the formula (XX),especially (XXa) are intermediates in the production of polymers, i.ethe compounds of the formula (XX) can be used in the production of thepolymers, comprising repeating units of formula (X).

Accordingly, the present invention is also directed to polymerscomprising repeating units of formula

whereinA^(1′) and A^(2′) are independently of each other a group of formula

wherein a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, and A⁵ areas defined above. The polymers of the present invention may be used inthe production of semiconductor devices. Accordingly, the presentinvention is also directed to semiconductor devices comprising a polymerof the present invention.

Advantageously, the compound of formula III, or an organic semiconductormaterial, layer or component, comprising the compound of formula III canbe used in organic photovoltaics (solar cells) and photodiodes, or in anorganic field effect transistor (OFET).

A mixture containing the compound of formula III results in asemi-conducting layer comprising the compound of formula III (typically0.1% to 99.9999% by weight, more specifically 1% to 99.9999% by weight,even more specifically 5% to 99.9999% by weight, especially 20 to 85% byweight) and at least another material. The other material can be, but isnot restricted to another compound of formula III, a polymer of thepresent invention, a semiconducting polymer, a non-conductive polymer,organic small molecules, carbon nanotubes, a fullerene derivative,inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂,ZnO etc.), conductive particles (Au, Ag etc.), insulator materials likethe ones described for the gate dielectric (PET, PS etc.).

Accordingly, the present invention also relates to an organicsemiconductor material, layer or component, comprising a compound offormula III and to a semiconductor device, comprising a compound offormula III and/or an organic semiconductor material, layer orcomponent.

The semiconductor is preferably an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor. Thestructure and the components of the OFET device has been described inmore detail above.

Accordingly, the invention provides organic photovoltaic (PV) devices(solar cells) comprising a compound of the formula III.

The structure of organic photovoltaic devices (solar cells) is, forexample, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.

The PV device comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) an anode (electrode),(f) a substrate.

The photoactive layer comprises the compounds of the formula III.Preferably, the photoactive layer is made of a compound of the formulaIII, as an electron donor and an acceptor material, like a fullerene,particularly a functionalized fullerene PCBM, as an electron acceptor.As stated above, the photoactive layer may also contain a polymericbinder. The ratio of the small molecules of formula III to the polymericbinder can vary from 5 to 95 percent. Preferably, the polymeric binderis a semicristalline polymer such as polystyrene (PS), high-densitypolyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate(PMMA).

The fullerenes useful in this invention may have a broad range of sizes(number of carbon atoms per molecule). The term fullerene as used hereinincludes various cage-like molecules of pure carbon, includingBuckminsterfullerene (C₆₀) and the related “spherical” fullerenes aswell as carbon nanotubes. Fullerenes may be selected from those known inthe art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullereneis selected from the range of C₆₉ to C₉₆. Most preferably the fullereneis C₆₉ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible toutilize chemically modified fullerenes, provided that the modifiedfullerene retains acceptor-type and electron mobility characteristics.The acceptor material can also be a material selected from the groupconsisting of another compounds of formula III, or any semi-conductingpolymer, such as, for example, a polymer of formula I, provided that thepolymers retain acceptor-type and electron mobility characteristics,organic small molecules, carbon nanotubes, inorganic particles (quantumdots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a compound of the formula III, as anelectron donor and a fullerene, particularly functionalized fullerenePCBM, as an electron acceptor. These two components are mixed with asolvent and applied as a solution onto the smoothing layer by, forexample, the spin-coating method, the drop casting method, theLangmuir-Blodgett (“LB”) method, the ink jet printing method and thedripping method. A squeegee or printing method could also be used tocoat larger surfaces with such a photoactive layer. Instead of toluene,which is typical, a dispersion agent such as chlorobenzene is preferablyused as a solvent. Among these methods, the vacuum deposition method,the spin-coating method, the ink jet printing method and the castingmethod are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)(f) optionally an extra electrode to match the energy level,(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(h) a photoactive layer,(i) optionally a smoothing layer,(j) an anode (electrode),(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or filmscomprising the compounds of the formula III can also be used alone ortogether with other materials in or as alignment layers in LCD or OLEDdevices, as described for example in US200310021913.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,    -   a drain electrode,    -   a gate electrode,    -   a semiconducting layer,    -   one or more gate insulator layers, and    -   optionally a substrate, wherein the semiconductor layer        comprises a compound of formula III.

The gate, source and drain electrodes and the insulating andsemiconducting layer in the OFET device may be arranged in any sequence,provided that the source and drain electrode are separated from the gateelectrode by the insulating layer, the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and asecond side, a gate electrode located on the first side of theinsulator, a layer comprising a compound of formula III located on thesecond side of the insulator, and a drain electrode and a sourceelectrode located on the polymer layer.

In a preferred embodiment, the deposition of at least one compound ofthe general formula III (and if appropriate further semiconductormaterials) is carried out by a gas phase deposition process (physicalvapor deposition, PVD). PVD processes are performed under high-vacuumconditions and comprise the following steps: evaporation, transport,deposition. It has been found that, surprisingly, the compounds of thegeneral formula III are suitable particularly advantageously for use ina PVD process, since they essentially do not decompose and/or formundesired by-products. The material deposited is obtained in highpurity. In a specific embodiment, the deposited material is obtained inthe form of crystals or comprises a high crystalline content. Ingeneral, for the PVD, at least one compound of the general formula IIIis heated to a temperature above its evaporation temperature anddeposited on a substrate by cooling below the crystallizationtemperature. The temperature of the substrate in the deposition ispreferably within a range from about 20 to 250° C., more preferably from50 to 200° C.

The resulting semiconductor layers generally have a thickness which issufficient for ohmic contact between source and drain electrodes. Thedeposition can be effected under an inert atmosphere, for example undernitrogen, argon or helium. The deposition is effected typically atambient pressure or under reduced pressure. A suitable pressure range isfrom about 10⁻⁷ to 1.5 bar.

The compound of the formula III is preferably deposited on the substratein a thickness of from 10 to 1000 nm, more preferably from 15 to 250 nm.In a specific embodiment, the compound of the formula III is depositedat least partly in crystalline form. For this purpose, especially theabove-described PVD process is suitable. Moreover, it is possible to usepreviously prepared organic semiconductor crystals. Suitable processesfor obtaining such crystals are described by R. A. Laudise et al. in“Physical Vapor Growth of Organic SemiConductors”, Journal of CrystalGrowth 187 (1998), pages 449-454, and in “Physical Vapor Growth ofCentimeter-sized Crystals of α-Hexathiophene”, Journal of Crystal Growth1982 (1997), pages 416-427, which are incorporated here by reference.

In addition, the polymers and compounds of the present invention may beused as IR absorbers.

Accordingly, the polymers and compounds of the present invention can beused inter alia for security printing, invisible and/or IR readable barcodes, the laser-welding of plastics, the curing of surface-coatingsusing IR radiators, the drying and curing of print, the fixing of tonerson paper or plastics, optical filters for plasma display panels, lasermarking of paper or plastics, the heating of plastics preforms, and forheat shielding applications.

In a further aspect, the invention provides a printing ink formulationfor security printing, comprising at least one polymer, or compound ofthe present invention, such as, for example, a polymer P-1, or P-2.

In a further aspect, the invention provides a security document,comprising a substrate and at least at least one polymer, or compound ofthe present invention. The security document may be a bank note, apassport, a check, a voucher, an ID- or transaction card, a stamp and atax label.

In a further aspect, the invention provides a security document,obtainable by a printing process, wherein a printing ink formulation isemployed that comprises at least one polymer, or compound of the presentinvention.

Advantageously, the polymers, or compounds of the present invention,such as, for example, polymer P-1, or P-2, may be used in a printing inkformulation for security printing.

In security printing, the polymers, or compounds of the presentinvention are added to a printing ink formulation. Suitable printinginks are water-based, oil-based or solvent-based printing inks, based onpigment or dye, for inkjet printing, flexographic printing, screenprinting, intaglio printing, offset printing, laser printing orletterpress printing and for use in electrophotography. Printing inksfor these printing processes usually comprise solvents, binders, andalso various additives, such as plasticizers, antistatic agents orwaxes. Printing inks for offset printing and letterpress printing areusually formulated as high-viscosity paste printing inks, whereasprinting inks for flexographic printing and intaglio printing areusually formulated as liquid printing inks with comparatively lowviscosity.

The printing ink formulation, especially for security printing,according to the invention preferably comprises

-   -   a) at least one polymer, or compound of the present invention,        such as, for example, a polymer P-1, or P-2,    -   b) a polymeric binder,    -   c) a solvent,    -   d) optionally at least one colorant, and    -   e) optionally at least one further additive.

Suitable components of printing inks are conventional and are well knownto those skilled in the art. Examples of such components are describedin “Printing Ink Manual”, fourth edition, Leach R. H. et al. (eds.), VanNostrand Reinhold, Wokingham, (1988). Details of printing inks and theirformulation are also disclosed in “Printing Inks”-Ullmann's Encyclopediaof Industrial Chemistry, Sixth Edition, 1999 Electronic Release. Aformulation of an IR-absorbing intaglio ink formulation is described inUS 20080241492 A1. The disclosure of the afore-mentioned documents isincorporated herein by reference.

The printing ink formulation according to the invention contains ingeneral from 0.0001 to 25% by weight, preferably from 0.001 to 15% byweight, in particular from 0.01 to 5% by weight, based on the totalweight of the printing ink formulation, of component a).

The printing ink formulation according to the invention contains ingeneral from 5 to 74% by weight, preferably from 10 to 60% by weight,more preferably from 15 to 40% by weight, based on the total weight ofthe printing ink formulation, of component b).

Suitable polymeric binders b) for the printing ink formulation accordingto the invention are for example selected from natural resins, phenolresin, phenol-modified resins, alkyd resins, polystyrene homo- andcopolymers, terpene resins, silicone resins, polyurethane resins,urea-formaldehyde resins, melamine resins, polyamide resins,polyacrylates, polymethacrylates, chlorinated rubber, vinyl esterresins, acrylic resins, epoxy resins, nitrocellulose, hydrocarbonresins, cellulose acetate, and mixtures thereof.

The printing ink formulation according to the invention can alsocomprise components that form a polymeric binder by a curing process.Thus, the printing ink formulation according to the invention can alsobe formulated to be energy-curable, e.g. able to be cured by UV light orEB (electron beam) radiation. In this embodiment, the binder comprisesone or more curable monomers andoligomers. Corresponding formulationsare known in the art and can be found in standard textbooks such as theseries “Chemistry & Technology of UV & EB Formulation for Coatings, Inks& Paints”, published in 7 volumes in 1997-1998 by John Wiley & Sons inassociation with SITA Technology Limited.

Suitable monomers and oligomers (also referred to as prepolymers)include epoxy acrylates, acrylated oils, urethane acrylates, polyesteracrylates, silicone acrylates, acrylated amines, and acrylic saturatedresins. Further details and examples are given in “Chemistry &Technology of UV & EB Formulation for Coatings, Inks & Paints”, VolumeII: Prepolymers & Reactive Diluents, edited by G Webster.

If a curable polymeric binder is employed, it may contain reactivediluents, i.e. monomers which act as a solvent and which upon curing areincorporated into the polymeric binder. Reactive monomers are typicallychosen from acrylates or methacrylates, and can be monofunctional ormultifunctional. Examples of multifunctional monomers include polyesteracrylates or methacrylates, polyol acrylates or methacrylates, andpolyether acrylates or methacrylates.

In the case of printing ink formulations to be cured by UV radiation, itis usually necessary to include at least one photoinitiator to initiatethe curing reaction of the monomers upon exposure to UV radiation.Examples of useful photoinitiators can be found in standard textbookssuch as “Chemistry & Technology of UV & EB Formulation for Coatings,Inks & Paints”, Volume III, “Photoinitiators for Free Radical Cationicand Anionic Polymerisation”, 2nd edition, by J. V. Crivello & K.Dietliker, edited by G. Bradley and published in 1998 by John Wiley &Sons in association with SITA Technology Limited. It may also beadvantageous to include a sensitizer in conjunction with thephotoinitiator in order to achieve efficient curing.

The printing ink formulation according to the invention contains ingeneral from 1 to 94.9999% by weight, preferably from 5 to 90% byweight, in particular from 10 to 85% by weight, based on the totalweight of the printing ink formulation, of a solvent c).

Suitable solvents are selected from water, organic solvents and mixturesthereof. For the purpose of the invention, reactive monomers which alsoact as solvents are regarded as part of the afore-mentioned bindercomponent b).

Examples of solvents comprise water; alcohols, e.g. ethanol, 1-propanol,2-propanol, ethylene glycol, propylene glycol, diethylene glycol andethoxy propanol; esters, e.g. ethyl acetate, isopropyl acetate, n-propylacetate and n-butyl acetate; hydrocarbons, e.g. toluene, xylene, mineraloils and vegetable oils, and mixtures thereof.

The printing ink formulation according to the invention may contain anadditional colorant d). Preferably, the printing ink formulationcontains from 0 to 25% by weight, more preferably from 0.1 to 20% byweight, in particular from 1 to 15% by weight, based on the total weightof the printing ink formulation, of a colorant d).

Suitable colorants d) are selected conventional dyes and in particularconventional pigments. The term “pigment” is used in the context of thisinvention comprehensively to identify all pigments and fillers, examplesbeing colour pigments, white pigments, and inorganic fillers. Theseinclude inorganic white pigments, such as titanium dioxide, preferablyin the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic leadcarbonate, antimony trioxide, lithopones (zinc sulfide+barium sulfate),or coloured pigments, examples being iron oxides, carbon black,graphite, zinc yellow, zinc green, ultramarine, manganese black,antimony black, manganese violet, Paris blue or Schweinfurt green.Besides the inorganic pigments the printing ink formulation of theinvention may also comprise organic colour pigments, examples beingsepia, gamboge, Cassel brown, toluidine red, para red, Hansa yellow,indigo, azo dyes, anthraquinonoid and indigoid dyes, and also dioxazine,quinacridone, phthalocyanine, isoindolinone, and metal complex pigments.Also suitable are synthetic white pigments with air inclusions toincrease the light scattering, such as the Rhopaque® dispersions.Suitable fillers are, for example, aluminosilicates, such as feldspars,silicates, such as kaolin, talc, mica, magnesite, alkaline earth metalcarbonates, such as calcium carbonate, in the form for example ofcalcite or chalk, magnesium carbonate, dolomite, alkaline earth metalsulfates, such as calcium sulfate, silicon dioxide, etc.

The printing ink formulation according to the invention may contain atleast one additive e). Preferably, the printing ink formulation containsfrom 0 to 25% by weight, more preferably from 0.1 to 20% by weight, inparticular from 1 to 15% by weight, based on the total weight of theprinting ink formulation, of at least one component e).

Suitable additives (component e)) are selected from plasticizers, waxes,siccatives, antistatic agents, chelators, antioxidants, stabilizers,adhesion promoters, surfactants, flow control agents, defoamers,biocides, thickeners, etc. and combinations thereof. These additivesserve in particular for fine adjustment of the application-relatedproperties of the printing ink, examples being adhesion, abrasionresistance, drying rate, or slip.

In particular, the printing ink formulation for security printingaccording to the invention preferably contains

-   -   a) 0.0001 to 25% by weight of at least one polymer, or compound        of the present invention, such as, for example, a polymer P-1,        or P-2,    -   b) 5 to 74% by weight of at least one polymeric binder,    -   c) 1 to 94.9999% by weight of at least one a solvent,    -   d) 0 to 25% by weight of at least one colorant, and    -   e) 0 to 25% by weight of at least one further additive,    -   wherein the sum of components a) to e) adds up to 100%.

The printing ink formulations according to the invention areadvantageously prepared in a conventional manner, for example by mixingthe individual components.

Primers can be applied prior to the printing ink formulation accordingto the invention. By way of example, the primers are applied in order toimprove adhesion to the substrate. It is also possible to applyadditional printing lacquers, e.g. in the form of a covering to protectthe printed image.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight.

Weight-average molecular weight (Mw) and polydispersity (MwMn=PD) aredetermined by Heat Temperature Gel Permeation Chromatography (HT-GPC)[Apparatus: GPC PL 220 from Polymer laboratories (Church Stretton, UK;now Varian) yielding the responses from refractive index (RI),Chromatographic conditions: Column: 3 “PLgel Olexis” column from PolymerLaboratories (Church Stretton, UK); with an average particle size of 13ìm (dimensions 300×8 mm I.D.) Mobile phase: 1,2,4-trichlorobenzenepurified by vacuum distillation and stabilised by butylhydroxytoluene(BHT, 200 mg/l), Chromatographic temperature: 150° C.; Mobile phaseflow: 1 ml/min; Solute concentration: about 1 mg/ml; Injection volume:200 ìl; Detection: RI, Procedure of molecular weight calibration:Relative calibration is done by use of a set of 10 polystyrenecalibration standards obtained from Polymer Laboratories (ChurchStretton, UK) spanning the molecular weight range from 1'930'000Da-5'050 Da, i.e., PS 1'930'000, PS 1'460'000, PS 1'075'000, PS 560'000,PS 330'000, PS 96'000, PS 52'000, PS 30'300, PS 10'100, PS 5'050 Da. Apolynomic calibration is used to calculate the molecular weight.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions.

EXAMPLES Example 1 Synthesis of Compound 6

a) 9.77 g AlCl₃ is suspended in 50 ml methylene chloride and then 5 g ofethyl chlorooxoacetate [4755-77-5] are added dropwise at −20° C. undernitrogen. Then 6.09 g of 2-bromothiophene [1003-09-4] are added dropwiseat −20° C. under stirring. After 1 h of stirring the reaction mixture ispoured on ice-water and the compound 1 is extracted with ethyl acetate.The product is purified by column chromatography. ¹H-NMR data (ppm,CDCl₃): 7.83 1H d, 7.11 1H d, 4.35 2H q, 1.37 3H t:

b) 9.07 g of the product 1 are suspended in 120 ml of ethanol and heatedto 70° C. At 60° C. a solution of NaOH (2.07 g) in water (2.07 g) isadded and the reaction mixture is stirred at 60° C. until no morestarting material is detected. Then the reaction mixture is acidified at20° C. with conc. HCl to give compound 2. ¹H-NMR data (ppm, CDCl₃): 9.651H very broad s, 8.18 1H d, 7.14 1H d;

c) Compound 2 is heated for 1 hour at 40° C. in excess thionyl chloride.Then the excess thionyl chloride is distilled off under reduced pressureto get compound 3. ¹H-NMR data (ppm, CDCl₃): 7.80 1H d, 7.18 1H d;

d) 10 g of compound 2 are dissolved in 50 ml of dry dimethylacetamideand cooled to −5° C. Then 5.51 g of thionyl chloride are added dropwise.After stirring for 10 minutes 5.44 g of 2-ethyl-1-hexylamine are addeddropwise over 30 minutes. At the end the reaction mixture is warmed toroom temperature and stirred for an additional 1 hour. The reactionmixture is quenched by the addition of water and the product isextracted with ethylacetate. After drying the organic phase andevaporation of the solvent, the product is purified by chromatographyover silica gel to give compound 4. ¹H-NMR data (ppm, CDCl₃): 7.99 1H d,7.18 1H m, 7.09 1H d, 3.25 2H t, 1.47 1H m, 1.34-1.23 8H m, 0.85 3H t,0.83 3H t.

d′) alternatively 2-Ethyl-1-hexylamine [104-75-6] and one equivalent ofcompound 3 are reacted 1 hour together with 1 equivalent oftriethylamine at room temperature in methylene chloride to give compound4. Compound 4 is purified by column chromatography.

e) 360 mg of sodium hydride (60% in mineral oil) are placed in areaction flask under nitrogen. Then 15 ml of dry tetrahydrofurane areadded at −30° C., followed by the addition of a solution of 460 mg of1,4-Cyclohexanedione [637-88-7] in 15 ml of dry tetrahydrofurane at −30°C. The reaction mixture is stirred for 30 minutes at −30° C. Then asolution of compound 4 in 15 ml of dry tetrahydrofurane is added dropwise at −30° C. The reaction mixture is stirred for another 30 minutesat −30° C. and then 1 hour at 0° C. The reaction is quenched by theaddition of water, and the product is extracted with ethyl acetate. Amixture of several compounds is obtained as shown by HPLC-MS, where twocompounds contained show the correct mass of 804 with area % of 50.81%and 25.37% respectively, which corresponds to 2 stereo isomers ofcompound 5. This mixture of compounds is directly used in the nextreaction.

f) 3.20 g of compound 5 (mixture containing stereo isomers) is dissolvedin 20 ml methylene chloride at room temperature, and then 0.25 ml ofconcentrated sulphuric acid are added drop wise under stirring. Thereaction mixture quickly turns to dark violet. The reaction mixture isstirred for another hour at room temperature. The reaction mixture iswashed with water, dried and evaporated. Compound 6 [=Cpd. 1-1] isobtained after column chromatography over silica gel. ¹H-NMR data (ppm,CDCl₃): 7.62 2H d, 7.05 2H d, 6.33 2H s, 3.54-3.38 4H m, 1.67 2H m,1.42-1.26 16H m, 0.91 6H t, 0.87 6H t;

Example 2 Synthesis of Compound 9

a) Compound 7 is obtained in analogy to compound 4 starting fromcompound [111-86-4] and compound 2. ¹H-NMR data (ppm, CDCl₃): 7.99 1H d,7.20 1H m, 7.09 1H d, 3.29 2H dxt, 1.51 2H m, 1.38-1.14 12H m. 0.80 3Ht:

b) Compound 8 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 7. Compound 8 is used directly in thesynthesis of compound 9 without purification.

c) Compound 9 [=Cpd. 1-2] is obtained in analogy to compound 6 startingfrom compound compound 8. ¹H-NMR data (ppm, CDCl₃): 7.68 2H d, 7.13 2Hd, 6.42 2H s, 3.66 4H t, 1.67 2H m, 1.53 2H m, 1.48-1.21 16H m, 0.86 6Ht;

Example 3 Synthesis of Compound 12

a) Compound 10 is obtained in analogy to compound 4 starting fromcompound [62281-05-4] and compound 2. ¹H-NMR data (ppm, CDCl₃): 7.99 1Hd, 7.18 1H m, 7.09 1H d, 3.23 2H t, 1.52 1H m, 1.35-1.15 24H m, 0.81 3Ht, 0.78 3H t;

b) Compound 11 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 10. Compound 11 is used directly in thesynthesis of compound 12 without purification.

c) Compound 12 [=Cpd. 1-3] is obtained in analogy to compound 6 startingfrom compound 11. ¹H-NMR data (ppm, CDCl₃): 7.62 2H d, 7.05 2H d, 6.352H s, 3.45 4H d, 1.72 2H m, 1.40-1.12 48H m, 0.80 6H t, 0.79 6H t;

Example 4 Synthesis of Compound 15

a) Compound 13 is obtained in analogy to compound 4 starting fromcompound [62281-07-6] and compound 2.

¹H-NMR data (ppm, CDCl₃): 8.08 1H d, 7.27 1H dxd, 7.18 1H d, 3.32 2H t,1.61 1H m, 1.38-1.25 40H m, 0.90 6H t.

[b) Compound 14 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 13. Compound 14 is used directly in thesynthesis of compound 15 without purification.

c) Compound 15 [=Cpd. 1-4] is obtained in analogy to compound 6 startingfrom compound 14. ¹H-NMR data (ppm, CDCl₃): 7.62 2H d, 7.05 2H d, 6.362H s, 3.46 4H d, 1.73 2H m, 1.40-1.12 80H m, 0.80 6H t, 0.79 6H t.

Example 5 Synthesis of Compound 18

a) Compound 16 is obtained in analogy to compound 4 starting fromammonium hydroxide [1336-21-6] and compound 2.

b) Compound 17 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 16. Compound 17 is used directly in thesynthesis of compound 18 without purification.

c) Compound 18 [=Cpd. 1-5] is obtained in analogy to compound 6 startingfrom compound 17.

Example 6 Synthesis of Compound 24

a) Compound 19 is obtained in analogy to compound 1 starting fromthiophene [110-02-1] and ethyl-chlorooxoacetate [4755-77-5].

b) Compound 20 is obtained in analogy to compound 2 by hydrolysis ofcompound 19.

c) Compound 21 is obtained in analogy to compound 3 from compound 20.

d) Compound 22 is obtained in analogy to compound 4 from compound 20 andthe amine [62281-05-4].

¹H-NMR data (ppm, CDCl₃): 8.33 1H d, 7.75 1H d, 7.19 1H dxd, 7.11 1Hdxd, 3.24 2H t, 1.53 1H m, 1.35-1.15 24H m, 0.81 6H t.

d′) Alternatively compound 22 is obtained in analogy to compound 4 fromcompound 21 and the amine [62281-05-4] via procedure d′.

e) Compound 23 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 22. Compound 23 is used directly in thesynthesis of compound 24 without purification.

f) Compound 24 [=Cpd. B-1] is obtained in analogy to compound 6 startingfrom compound 23.

¹H-NMR data (ppm, CDCl₃): 8.04 2H d, 7.53 2H d, 7.20 2H dxd, 6.61 2H s,3.58 4H d, 1.86 2H broad s, 1.50-1.20 48H m, 0.88 12H t.

Example 7 Synthesis of Compound 25

0.5 g of compound 15, 0.272 g of bithiophene-boronic acid pinacol ester[479719-88-5], 4 mg palladium(II)acetate and 19 mg of2-(di-tert-butyl-phsophino)-1-phenyl-1H-pyrrole [672937-61-0] are placedin a reactor under argon. 20 ml of degassed tetrahydrofurane is addedand the mixture is heated to reflux. Then 107 mg of lithium hydroxydemonohydrate are added. The reaction is stirred 2 hours at reflux. Thecolor changes from violet to green. Then the reaction mixture is pouredon water and the product is extracted with methylene chloride. Theorganic phase is dried and evaporated. Compound 25 [=Cpd. B-8] isobtained after purification by chromatography over silica gel. ¹H-NMRdata (ppm, CDCl₃): 7.81 2H d, 7.14 2H d, 7.06 4H d, 7.01 2H d, 6.96-6.914H m, 6.35 2H s, 3.45 4H d, 1.71 2H m, 1.40-1.10 80H m, 0.78 6H t, 0.776H t;

Example 8 Synthesis of Compound 26

0.7 g of compound 12, 0.54 g of bithiophene-boronic acid pinacol ester[479719-88-5], 13 mg of Pd₂(dba)_(3 [51364)-51-3] and 13 mg oftri-tert-butyl-phosphino-tetra-fluoroborate are placed in a reactorunder argon. Then 14 ml of degassed tetrahydrofurane are added and thereaction mixture is stirred some minutes at 45° C. Then a degassedsolution of 776 mg of K₃PO₄ in 1.4 ml of water is added, and thereaction mixture is then stirred for 1 hour at reflux. The color of thereaction mixture is turning from violet to green. The reaction mixtureis poured into methanol. The resulting solid is filtered and washed withmethanol and water. The solid is then dissolved in hot1,2-dichlorobenzene and mixed with silica gel. The cooled slurry is thenfiltered and washed with 1,2-dichlorobenzene. The silica powder is thenadded to a Soxhlet cartridge and compound 26 [=Cpd. B-3] is obtained bySoxhlet extraction with chloroform. Finally the product is purified byrecrystallization from chloroform. ¹H-NMR data (ppm, CDCl₃): 7.86 2H d,7.15 2H d, 7.12 2H d, 7.11-7.08 4H m, 6.95 2H dxd, 6.47 2H s, 3.51 4H d,1.77 2H m, 1.40-1.12 48H m, 0.77 6H t, 0.75 6H t;

Example 9 Synthesis of Compound 27

Compound 27 is synthesized in analogy to compound 26 starting fromcompound 12 and thiopheneboronicacid-pinacolester [193978-23-3].Compound 27 [=Cpd. B-2] is then obtained after purification bychromatography over silica gel. ¹H-NMR data (ppm, CDCl₃): 7.85 2H d,7.22-7.19 4H m, 7.15 2H d, 6.97 2H dxd, 6.47 2H s, 3.49 4H d, 1.76 2H m,1.40-1.12 48H m, 0.78 6H t, 0.77 6H t;

Example 10 Synthesis of Polymer 28

0.8 g of the dibromo compound 15, 0.228 g of the bis-boronicacidestercompound [175361-81-6], 0.8 mg palladium(II)acetate, and 4.6 mg of2-(Di-tert-butyl-phosphino)-1-phenylindole [740815-37-6] are placed in areactor. The reactor is degassed with Argon and then 12 ml of degassedtetrahydrofurane are added. The reaction mixture is heated to reflux,and then 170 mg of lithium hydroxide monohydrate are added. The reactionmixture is refluxed for another two hours. The dark solution is thenpoured on a mixture of ethanol-water where the polymer precipitates. Themixture is filtered and the polymer is washed with water. Then thepolymer is dissolved in chloroform and washed three times with water.The polymer is then precipitated by adding acetone, filtered and dried.The polymer 28 [=Polymer P-1] is then Soxhlet fractionated with THF(HT-GPC: Mw 102293, PD 4.33) and chloroform (HT-GPC: Mw 121263, PD4.18).

Example 11 Synthesis of Compound 12

1 g of compound 24 is dissolved in CHCl₃. Then 2 equivalents ofN-bromo-succinimid and 0.035 equivalents of 70% perchloric acid areadded and the reaction mixture is stirred for 4 h at 0° C. The organicphase is washed with water, dried and evaporated. The product 12 [=Cpd.1-6] is purified by column chromatography on silica gel. ¹H-NMR data(ppm, CDCl₃): 7.62 2H d, 7.05 2H d, 6.35 2H s, 3.45 4H d, 1.72 2H m,1.40-1.12 48H m, 0.80 6H t, 0.79 6H t;

Example 12 Synthesis of Compound 34

a) Compound 32 is obtained in analogy to compound 4 from compound[1467-70-5] and the amine [62281-07-6]. ¹H-NMR data (ppm, CDCl₃): 8.211H d, 7.77 1H d, 7.28 1H s, 6.64 1H dxd, 3.31 2H dxd, 1.61 1H m,1.40-1.12 40H m, 0.89 6H t.

b) Compound 33 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 32. Compound 33 is used directly in thesynthesis of compound 34 without purification.

c) Compound 34 [=Cpd. B-6] is obtained in analogy to compound 6 startingfrom compound 33.

Example 13 Synthesis of Compound 35

Compound 35 [=Cpd. 1-8] is obtained in analogy to example 11 startingfrom compound 34 but without adding perchloric acid.

Example 14 Synthesis of Compound 41

a) Compound 36 is obtained in analogy to compound 1 starting fromthienothiophene [251-41-2] and ethyl-chlorooxoacetate [4755-77-5].¹H-NMR data (ppm, CDCl₃): 8.39 1H s, 7.74 1H d, 7.36 1H d, 4.44 2H q,1.46 3H t.

b) Compound 37 is obtained in analogy to compound 2 by hydrolysis ofcompound 36. ¹H-NMR data (ppm, DMSO-d6): 8.15 1H s, 7.94 1H d, 7.49 1Hd, OH peak not visible.

c) Compound 38 is obtained in analogy to compound 3 from compound 37.

d) Compound 39 is obtained in analogy to compound 4 from compound 37 andthe amine [62281-07-6].

d′) Alternatively compound 39 is obtained in analogy to compound 4 fromcompound 38 and the amine [62281-07-6] via procedure d′.

e) Compound 40 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 39. Compound 40 is used directly in thesynthesis of compound 41 without purification.

f) Compound 41 [=Cpd. B-7] is obtained in analogy to compound 6 startingfrom compound 40.

Example 15 Synthesis of Compound 42

Compound 42 [=Cpd. 1-7] is obtained in analogy to example 11 startingfrom compound 41.

Example 16 Synthesis of Compound 44

a) Compound 43 is obtained in analogy to compound 25 starting fromcompound 15 by using only 1 equivalent of compound [479719-88-5].

b) Compound 44 [=Cpd. C-1] is obtained in analogy to the method ofcompound 25 starting from two equivalents of compound 43 and 1equivalent of compound [175361-81-6]. The ligand used is2-(di-tert-butylphosphino)-1-phenylindole instead of2-(di-tert-butyl-phsophino)-1-phenyl-1H-pyrrole [672937-61-0]

Application Example 1 Application of the Semiconducting Polymer 28

The semiconductor thin film is prepared by spin-coating the polymer ofthe formula 28 obtained in example 10 in a 0.5% (w/w) solution inchloroform. The spin coating is accomplished at a spinning speed of 3000rpm (rounds per minute) for about 20 seconds in ambient conditions. Thedevices are evaluated as deposited and after being annealed at 100° C.for 15 minutes.

Transistor Performance

The transistor behavior is measured on an automated transistor prober(TP-10, CSEM Zürich) and showed clear transistor behavior.

Application Example 2 Photovoltaic Application of the SemiconductingPolymer 28 [=Polymer P-1]

The solar cell has the following structure: Al electrode/LiFlayer/organic layer, including compound of theinvention/[poly(3,4-ethylenedioxy-thiophene)(PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate.The solar cells are made by spin coating a layer of the PEDOT-PSS on apre-patterned ITO on glass substrate. Then a 1:1 mixture of the polymerof formula 28 (1% by weight): [70]PCBM (a substituted C₂₀ fullerene) isspin coated (organic layer). LiF and Al are sublimed under high vacuumthrough a shadow-mask.

Solar Cell Performance

The solar cell is measured under a solar light simulator. Then with theExternal Quantum Efficiency (EQE) graph the current is estimated underAM1.5 conditions.

The OPV performance of Polymer P-1 is shown in the table below:

Example Semiconductor J_(sc), mA/cm² Voc, V FF, % η, % 11 Polymer P-1−1.73 0.66 66.4 0.75

Example 17 Synthesis of Polymer 48 [=Polymer P-2]

a) Compound 45 is obtained according to compound 4 starting fromcompound [62281-06-5] and compound 2. ¹H-NMR data (ppm, CDCl₃): 8.08 1Hd, 7.26 1H dxd, 7.19 1H d, 3.32 2H t, 1.61 1H broad s, 1.38-1.25 32H m,0.90 6H t.

b) Compound 46 is obtained according to compound 5 starting fromcompound [637-88-7] and compound 45. Compound 46 is used directly in thesynthesis of compound 47 without purification.

c) Compound 47 is obtained according to compound 6 starting fromcompound 46. ¹H-NMR data (ppm, CDCl₃): 7.62 2H d, 7.05 2H d, 6.36 2H s,3.46 4H d, 1.72 2H broad s, 1.40-1.12 64H m, 0.79 12H t.

d) Polymer 48 [=polymer P-2] is synthesized according to the method ofcompound 28 starting from compound 47 andthiophene-di-boronicacid-pinacolester [175361-81-6] in a 1:1 ratio. Theproduct is fractionated in a Soxhlet apparatus with tetrahydrofurane andchloroform. The chloroform fraction gives the following HT-GPC result:Mw 79192, PD 4.41.

Example 18 Synthesis of Compound 50 [=Cpd. C-2]

a) 0.7 g of compound 24 is dissolved in CHCl₃. Then 1 equivalent ofN-bromo-succinimid is added and the reaction mixture is stirred for 1 hat −10° C. and for 1 hour at 0° C. The organic phase is washed withwater, dried and evaporated. The product is purified by columnchromatography on silica gel. ¹H-NMR data (ppm, CDCl₃): 7.97 1H d, 7.621H d, 7.46 1H d, 7.13 1H dxd, 7.06 1H d, 6.54 1H s, 6.36 1H s, 3.49 4Hd, 1.76 2H broad s, 1.45-1.15 48H m, 0.80 12H t.

b) 308 mg of the monobromo compound 49 [=Cpd. 1-3], 58.9 mg of thebis-boronicacidester compound [175361-81-6], 0.4 mgpalladium(II)acetate, and 2.4 mg of2-(Di-tert-butyl-phosphino)-1-phenylindole [740815-37-6] are placed in areactor. The reactor is degassed with Argon and then 5 ml of degassedtetrahydrofurane are added. The reaction mixture is heated to reflux,and then 88 mg of lithium hydroxide monohydrate are added. The reactionmixture is refluxed for another two hours. The dark solution is thenpoured on water and the product is extracted with chloroform. Theproduct is purified by chromatography over silicagel to give thecompound 50 [=cpd. C-2]. ¹H-NMR data (ppm, CDCl₃): 8.03 2H d, 7.91 2H d,7.50 2H d, 7.21 2H d, 7.18 2H dxd, 7.17 2H s, 6.53 2H s, 6.48 2H s, 3.594H d, 3.52 4H d, 1.82 4H broad s, 1.50-1.15 96H m, 0.86 24H t.

Example 19 Synthesis of Polymer 51 [=Polymer P-4]

Polymer 51 [=polymer P-4] is synthesized according to the method ofcompound 28 starting from compound 15 andthieno-thiophene-di-boronicacid-pinacolester [924894-85-9] in a 1:1ratio. The product is fractionated in a Soxhlet apparatus withtetrahydrofurane and chloroform.

Example 20 Synthesis of Polymer 52 [=Polymer P-5]

Polymer 52 [=polymer P-5] is synthesized according to the method ofcompound 28 starting from compound 15 andphenyl-di-boronicacid-pinacolester [99770-93-1] in a 1:1 ratio. Theproduct is fractionated in a Soxhlet apparatus with tetrahydrofurane andchloroform.

Example 21 Synthesis of Polymer 53 [=Polymer P-6]

Compound 53 [=polymer P-6] is synthesized according to the method ofcompound 28 starting from compound 15 and2,6-naphthyl-di-boronicacid-pinacolester [849543-98-2] in a 1:1 ratio.The product is fractionated in a Soxhlet apparatus with tetrahydrofuraneand chloroform.

Example 22 Synthesis of Polymer 54 [=Polymer P-7]

Polymer 54 [=polymer P-7] is synthesized according to the method ofcompound 28 starting from compound 15 andcarbazol-di-boronicacid-pinacolester [476360-83-5] in a 1:1 ratio. Theproduct is fractionated in a Soxhlet apparatus with tetrahydrofurane andchloroform.

Example 23 Synthesis of Polymer 55 [=Polymer P-8]

Polymer 55 [=polymer P-8] is synthesized according to the method ofcompound 28 starting from compound 15 andbenzodithiophene-di-boronicacid-pinacolester [1295502-42-9] in a 1:1ratio. The product is fractionated in a Soxhlet apparatus withtetrahydrofurane and chloroform.

Example 24 Synthesis of Polymer 56 [=Polymer P-9]

Polymer 56 [=polymer P-9] is synthesized according to the method ofcompound 28 starting from compound 15 andbenzodithiophene-di-boronicacid-pinacolester [1256165-36-2] in a 1:1ratio. The product is fractionated in a Soxhlet apparatus withtetrahydrofurane and chloroform.

Example 25 Synthesis of Polymer 57 [=Polymer P-10]

Polymer 57 [=polymer P-10] is synthesized according to the method ofcompound 28 starting from compound 15 andbi-thiophene-di-boronicacid-pinacolester [239075-02-6] in a 1:1 ratio.The product is fractionated in a Soxhlet apparatus with tetrahydrofuraneand chloroform.

Example 26 Synthesis of Compound 58 [=Compound B-18]

Compound 58 is synthesized in analogy to the synthesis described forcompound 24 in Example 6, using 1-octylamine instead of2-hexyldecylamine. ¹H-NMR data (ppm, CDCl₃): 8.01 2H d, 7.54 2H d, 7.212H dxd, 6.58 2H s, 3.69 4H t, 1.72 4H txt, 1.50-1.25 20H m, 0.89 6H t.

Example 27 Synthesis of Compound 59 [=Compound B-19]

Compound 59 is synthesized in analogy to the synthesis described forcompound 24 in Example 6, using 1-butylamine instead of2-hexyldecylamine. ¹H-NMR data (ppm, CDCl₃): 8.01 2H d, 7.54 2H d, 7.212H dxd, 6.59 2H s, 3.72 4H t, 1.71 4H txt, 1.46 4H txt, 1.01 6H t.

Example 28 Synthesis of Compound 60

Compound 60 is synthesized in analogy to the synthesis described forcompound 24 in Example 6, using 1-methylamine instead of2-hexyldecylamine.

Application Example 3 Bottom Gate Bottom Contacts Field EffectTransistor (BGBC) Semiconductor Film Deposition:

Siliconwafers (Si n⁻⁻(425±40 μm)) with a 230 nm thick SiO₂ dielectricand patterned indium tin oxide (15 nm) gold (30 nm) contacts (L=20, 10,5, 2.5 μm, W=0.01 m; Fraunhofer IPMS (Dresden)) are prepared by washingwith acetone and i-propanol followed by oxygen plasma treatment for 30minutes.

The substrates are transferred in a glove box. An octylsilane (OTS)monolayer is grown on the dielectric surface by putting the substratesin a 50 mM solution of octyltrichlorosilane (OTS) in toluene for 1 h.After monolayer growth, the substrates are washed with toluene to removephysisorbed silane.

The semiconductor is dissolved in a proper solvent in a concentration0.75% by weight at 80° C. and spin-coated at 1500 rpms for 60 s onto thesubstrates.

OFET Measurement:

OFET transfer and output characteristics are measured on an Agilent4155C semiconductor parameter analyzer. The devices are annealed in aglovebox at 150° C. for 15 minutes before the measurements are done in aglove box under a nitrogen atmosphere at room temperature. For p-typetransistors the gate voltage (V_(g)) varies from 10 to −30 V and atdrain voltage (V_(d)) equal to −3 and −30V for the transfercharacterisation. For the output characterization V_(d) is varied from 0to −30V at V_(g)=0, −10, −20, −30 V. Mobilities reported are thesaturation mobilities at V_(d)=−30V.

For n-type transistors the gate voltage (V_(g)) varies from −10 to 30 Vand at drain voltage (V_(d)) equal to 3 and 30V for the transfercharacterisation. For the output characterization V_(d) is varied from 0to 30V at V_(g)=0, 10, 20, 30 V. Mobilities reported are the saturationmobilities at V_(d)=30V.

The OFET performance of Cpd. B-3 and C-2 as well as Polymers P-1 and P-2is shown in the table below:

Appl. Semi- OFET- Sat. Mobility, Example conductor Solvent type cm²/VSOn/off 3a Cpd. B-3 CHCl₃ p 5.0 · 10⁻⁴ 1.0 · 10⁺⁴ 3b Cpd. B-3 CHCl₃ n 3.7· 10⁻⁴ 2.4 · 10⁺³ 3c Cpd. B-2 CHCl₃ p 6.6 · 10⁻⁴ 1.5 · 10⁺³ 3d Cpd. C-2Toluene p 3.0 · 10⁻⁶ 4.0 · 10⁺² 3e Polymer P-1 Toluene p 5.1 · 10⁻³ 1.0· 10⁺² 3f Polymer P-1 CHCl₃ p 7.9 · 10⁻³ 5.4 · 10⁺² 3g Polymer P-1 CHCl₃n 1.1 · 10⁻² 1.3 · 10⁺² 3h Polymer P-2 Toluene p 6.1 · 10⁻³ 1.0 · 10⁺²3i Polymer P-2 CHCl₃ p 1.5 · 10⁻² 1.9 · 10⁺³ 3j Polymer P-2 CHCl₃ n 1.8· 10⁻² 6.2 · 10⁺²

The polymers P-1 and P-2 have good solubility in organic solvents andexcellent film-forming properties. The OFETs of Application Examples 3eto 3j, where the semiconductor layer consists of polymer P-1, or P-2,show good processibility, equally good hole and electron mobilities.

The compounds B-2, B-3 and C-2 have excellent solubility in organicsolvents and excellent film-forming properties (excellent filmuniformity).

Application Example 4 Top Gate Bottom Contacts Field Effect Transistor(TGBC FET) Substrate Preparation:

For TGBC FETs polyethylene terephthalate (PET) substrates withlithographically patterned 50 nm gold (Au) contacts covered withphotoresist are used. Substrates are prepared by standard cleaning inacetone and ethanol and dried at 60° C. for 30 minutes.

Transistor Preparation:

The semiconductor polymer P-1 is dissolved in chloroform (0.75 wt %) at50° C. for 4 h, filtered through a 0.45 μm filter, spun to achieve a 50nm layer thickness and dried for 30 seconds at 80° C.

Immediately after a 500 nm thick layer of a dielectric (Allresist GmbH,4% 950K polymethyl methacrylate (PMMA) in butylacetate: ethyllacetatesolvent mixture) has been spin-coated and dried for 2 minutes at 80° C.120 nm thick gold contacts are evaporated through a shadow mask as gatecontacts.

The OFET performance of polymer P-1 is summarized in the table below:

Sat. Mobility, rel. Sigma Example Semiconductor cm²/VS Mobility Sat, % 4P-1 0.0088 3

Semiconducting polymer P-1 of application example 4 shows goodprocessability, moderate mobility and excellent film uniformity, whenused for the preparation of a TGBC FET.

Example 29 Synthesis of Compound 65

a) Compound 61 is obtained in analogy to compound 1 starting frombi-thiophene [492-97-7] and ethyl-chlorooxoacetate [4755-77-5]. ¹H-NMRdata (ppm, CDCl₃): 8.04 1H d, 7.38 2H d, 7.20 1H d, 7.07 1H dxd, 4.43 2Hq, 1.43 3H t.

b) Compound 62 is obtained in analogy to compound 2 by hydrolysis ofcompound 61. ¹H-NMR data (ppm, CDCl₃): 8.49 1H d, 7.47 2H dd, 7.32 1H d,7.12 1H dxd, OH signal not visible.

c) Compound 63 is obtained in analogy to compound 4 from compound 62 andthe amine [111-86-4].

¹H-NMR data (ppm, CDCl₃): 8.31 1H d, 7.43 1H d, 7.39 1H d, 7.37 1H broads, 7.26 1H d, 7.11 1H dxd, 3.39 2H dxt, 1.62 2H txt, 1.45-1.21 10H m,0.90 3H t.

e) Compound 64 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 63. Compound 64 is used directly in thesynthesis of compound 65 without purification.

f) Compound 65 [=Cpd. B-9] is obtained in analogy to compound 6 startingfrom compound 64. ¹H-NMR data (ppm, CDCl₃): 7.93 2H d, 7.31 4H d+d, 7.262H d, 7.08 2H dxd, 6.56 2H s, 3.72 4H t, 1.76-1.69 4H m, 1.50-1.25 20Hm, 0.88 6H t.

Example 30 Synthesis of Compound 68

a) Compound 66 is obtained in analogy to compound 4 starting fromammonium hydroxide [1336-21-6] and compound 20. ¹H-NMR data (ppm,CDCl₃): 8.43 1H d, 7.86 1H d, 7.21 1H dxd, 7.19 1H broad s, 5.74 1Hbroad s.

b) Compound 67 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 66. Compound 67 is used directly in thesynthesis of compound 68 without purification.

c) Compound 68 [=Cpd. B-10] is obtained in analogy to compound 6starting from compound 67.

¹H-NMR data (ppm, DMF-d7): 10.51 2H s, 8.18 2H d, 8.06 2H d, 7.47 2Hdxd, 6.96 2H s.

Example 31 Synthesis of Compound 70 [=Compound B-11]

a) 1.086 g of compound 68 are suspended together with 1.714 g ofpotassium carbonate in 8 ml of dimethylformamide. The reaction mixtureis heated to 50° C. and 1.5 g of allylbromide are added. The reactionmixture is then heated at 70° C. over night. Then the reaction mixtureis cooled to room temperature and poured into water. The product isextracted with ethyl acetate. The organic phase is dried over MgSO₄,filtered and evaporated. The residue is purified by columnchromatography over silica gel and a product of formula 69 [=Cpd. B-11]is obtained. ¹H-NMR data (ppm, CDCl₃): 8.01 2H d, 7.54 2H d, 7.20 2Hdxd, 6.64 2H s, 5.94-5.85 2H m, 5.39-5.30 2H m, 4.36 4H d.

b) 220 mg of compound 69 are dissolved together with 170 mg of thepentamethyldisiloxane [1438-82-0] in 5 ml of dry toluene under nitrogen.Then 1 drop of Karstedt-catalyst is added and the reaction mixture isheated at reflux temperature over night. Then the solvent is evaporatedand the product is purified over silica gel to give a compound offormula 70 [=Cpd. B-12].

¹H-NMR data (ppm, CDCl₃): 8.00 2H d, 7.54 2H d, 6.94 2H dxd, 6.60 2H s,3.69 4H t, 1.77-1.71 4H m, 0.65-0.59 4H m, 0.11 12H s, 0.05 18H s.

Example 32 Synthesis of Compound 73

a) Compound 71 is obtained in analogy to compound 4 starting fromammonium hydroxide [1336-21-6] and compound 37.

¹H-NMR data (ppm, CDCl₃): 8.77 1H s, 7.76 1H d, 7.34 1H d, 7.18 1H broads, 5.66 1H broad s.

b) Compound 72 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 71. Compound 72 is used directly in thesynthesis of compound 73 without purification.

c) Compound 73 [=Cpd. B-13] is obtained in analogy to compound 6starting from compound 72.

The MS spectrum (APCI positive mode) confirms the molecular mass of 462.

Example 33 Synthesis of Compound 76

a) Compound 74 is obtained in analogy to compound 4 starting fromammonium hydroxide [1336-21-6] and compound [1467-70-5]. ¹H-NMR data(ppm, CDCl₃): 8.14 1H d, 7.78 1H d, 7.18 1H broad s, 6.65 1H dxd, 5.831H broad s.

b) Compound 75 is obtained in analogy to compound 5 starting fromcompound [637-88-7] and compound 74. Compound 75 is used directly in thesynthesis of compound 76 without purification.

c) Compound 76 [=Cpd. B-14] is obtained in analogy to compound 6starting from compound 75.

The MS spectrum (APCI positive mode) confirms the molecular mass of 318.

Example 34 Synthesis of Compound 77

Compound 77 [=Cpd. B-15] is obtained in analogy to compound 69 startingfrom compound 68 and the decyltetradecyliodide [1143585-16-3].

¹H-NMR data (ppm, CDCl₃): 8.03 2H d, 7.52 2H d, 7.19 2H dxd, 6.60 2H s,3.57 4H d, 1.86 2H broad s, 1.45-1.20 80H m, 0.88 12H t.

Example 35 Synthesis of Compound 80

a) Compound 78 is obtained according to compound 4 starting fromcompound [62281-06-5] and compound [1467-70-5]. ¹H-NMR data (ppm,CDCl₃): 8.21 1H d, 7.77 1H d, 7.28 1H broad s, 6.64 1H dxd, 3.31 2H dxd,1.61 1H broad s, 1.38-1.22 32H m, 0.90 6H t.

b) Compound 79 is obtained according to compound 5 starting fromcompound [637-88-7] and compound 78. Compound 479 is used directly inthe synthesis of compound 80 without purification.

c) Compound 80 [=Cpd. B-16] is obtained according to compound 6 startingfrom compound 79. ¹H-NMR data (ppm, CDCl₃): 7.61 2H d, 7.42 2H d, 6.302H s, 6.60 2H dxd, 3.54 4H d, 1.86 2H broad s, 1.45-1.12 64H m, 0.88 12Ht.

Example 36 Synthesis of Compound 83

a) Compound 81 is obtained according to compound 4 starting fromcompound [62281-06-5] and compound 37. ¹H-NMR data (ppm, CDCl₃): 8.77 1Hs, 7.75 1H d, 7.33 1H d, 7.31 1H broad s, 3.35 2H dxd, 1.63 1H broad s,1.45-1.25 32H m, 0.90 6H t.

b) Compound 82 is obtained according to compound 5 starting fromcompound [637-88-7] and compound 81. Compound 82 is used directly in thesynthesis of compound 83 without purification.

c) Compound 83 [=Cpd. B-17] is obtained according to compound 6 startingfrom compound 82. ¹H-NMR data (ppm, CDCl₃): 8.36 2H s, 7.52 2H d, 7.262H d, 6.64 2H s, 3.61 4H d, 1.88 2H broad s, 1.50-1.20 64H m, 0.86 12Ht.

Example 37 Synthesis of Compound 84

Compound 84 [=Cpd. I-11] is obtained in analogy to example 13 startingfrom compound 80.

Example 38 Synthesis of Compound 85

Compound 85 [=Cpd. 1-12] is obtained in analogy to example 15 startingfrom compound 83, without the addition of perchloric acid. ¹H-NMR data(ppm, CDCl₃): 8.20 2H s, 7.18 2H s, 6.42 2H s, 3.51 4H d, 1.77 2H broads, 1.48-1.20 64H m, 0.88 12H t.

Example 39 Synthesis of Polymer 86 [=Polymer P-11]

Polymer 86 [=polymer P-11] is synthesized according to the method ofcompound 28 starting from compound 35 andthieno-thiophene-di-boronicacid-pinacolester [924894-85-9] in a 1:1ratio. The product is fractionated in a Soxhlet apparatus withtetrahydrofurane and chloroform.

Example 40 Synthesis of Polymer 87 [=Polymer P-12]

Polymer 87 [=polymer P-12] is synthesized according to the method ofcompound 28 starting from compound 35 andthiophene-di-boronicacid-pinacolester [175361-81-6] in a 1:1 ratio. Theproduct is fractionated in a Soxhlet apparatus with tetrahydrofurane andchloroform.

Example 41 Synthesis of Polymer 88 [=Polymer P-13]

Polymer 88 [=polymer P-13] is synthesized according to the method ofcompound 28 starting from compound 35 andbi-thiophene-di-boronicacid-pinacolester [239075-02-6] in a 1:1 ratio.The product is fractionated in a Soxhlet apparatus with tetrahydrofuraneand chloroform.

Example 42 Synthesis of Polymer 89 [=Polymer P-14]

Polymer 89 [=polymer P-14] is synthesized according to the method ofcompound 28 starting from compound 42 andthiophene-di-boronicacid-pinacolester [175361-81-6] in a 1:1 ratio. Theproduct is fractionated in a Soxhlet apparatus with tetrahydrofurane andchloroform.

1. A polymer, comprising a unit of formulaAr³_(c)Ar²_(b)Ar¹_(a)YAr^(1′)_(a′)Ar^(2′)_(b′)Ar^(3′)_(c′)(I), wherein Y is a group of formula

a is 1, 2, or 3, a′ is 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; U¹ is O, S, or NR¹; U² is O,S, or NR²; T¹ and T² are each independently hydrogen, halogen, hydroxyl,cyano, —COOR¹⁰³, —OCOR¹⁰³, —NR¹¹²COR¹⁰³, —CONR¹¹²R¹¹³, OR^(103′),—SR^(103′), —SOR^(103′), —SO₂R^(103′), —NR¹¹²SO₂R^(103′), —NR¹¹²R¹¹³,C₁-C₂₅alkyl, which may be substituted by E and/or interrupted by D,C₅-C₁₂cycloalkyl, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl whichis substituted by G; R¹ and R² may be the same or different and are eachindependently selected from hydrogen, a C₁-C₁₀₀alkyl group which canoptionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—, a C₂-C₁₀₀alkenyl group which can optionally besubstituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group,or a siloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—, a C₃-C₁₀₀alkinyl groupwhich can optionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy,halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—, a C₃-C₁₂cycloalkyl group which can optionally besubstituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group,or a siloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—, a C₆-C₂₄aryl group whichcan optionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group, aC₂-C₂₀heteroaryl group which can optionally be substituted withC₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group, a—CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group, or —COO—C₁-C₁₈alkylgroup; R³⁹ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl,or C₁-C₁₈alkanoyl, R¹⁰³ and R^(103′) are each independentlyC₁-C₁₀₀alkyl, C₁-C₂₅alkyl substituted by E and/or interrupted with D,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G; Ar¹ andAr^(1′) are each independently

wherein X is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

Ar², Ar^(2′), Ar³ and Ar^(3′) have independently of each other themeaning of Ar¹, or are independently of each other

or

wherein X¹ is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—,—C(R¹⁰⁶)(R¹⁰⁹)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are each independently hydrogen, halogen, halogenatedC₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which may optionally be interrupted by an oxygen or sulphur atom;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹⁰⁴ and R^(104′) are eachindependently hydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, orC₆-C₂₄aryl or C₂-C₂₀heteroaryl; R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′)are each independently hydrogen, halogen, halogenated C₁-C₂₅alkyl,especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which mayoptionally be interrupted by an oxygen or sulphur atom; C₇-C₂₅arylalkyl,or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are each independentlyhydrogen, C₁-C₂₅alkyl, which may optionally be interrupted by an oxygen,or sulphur atom; or C₇-C₂₅arylalkyl, R⁸ and R^(8′) are eachindependently hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen or sulphur atom; or C₇-C₂₅arylalkyl, R¹¹ andR^(11′) are each independently C₁-C₂₅alkyl group, which can besubstituted with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are eachindependently hydrogen, halogen, cyano, C₁-C₂₅alkyl, which mayoptionally be interrupted by an oxygen, or sulphur atom, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or =—R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or atri(C₁-C₈alkyl)silyl group; R¹⁰⁴ and R^(104′) are each independentlyhydrogen, C₁-C₁₈alkyl, C₆-C₁₀aryl, which may optionally be substitutedby G, or C₂-C₈heteroaryl, which may optionally be substituted by G,R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are each independently hydrogen,halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by anoxygen or sulphur atom; C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy; R¹⁰⁷ ishydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which is substitutedby C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl; C₁-C₂₅alkyl,which may be interrupted by —O—, or —S—; or —COOR¹⁰³; R¹⁰⁸ and R¹⁰⁹ areeach independently H, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by Eand/or interrupted by D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹ together form a group of formula═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹ are each independently H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, or R¹⁰⁸ and R¹⁰⁹ togetherform a five or six membered ring, which optionally can be substituted byC₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl; D is —CO—, —COO—, —S—, —O—,or NR¹¹²—; E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³,—CONR¹¹²R¹¹³, or halogen; G is E, or C₁-C₁₈alkyl; R¹¹² and R¹¹³ are eachindependently H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—; R¹¹⁴ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, whichmay optionally be interrupted by an oxygen, or sulphur atom; R¹¹⁵ andR^(115′) are each independently hydrogen, halogen, cyano, C₁-C₂₅alkyl,which may optionally be interrupted by an oxygen, or sulphur atom,C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or =—R¹¹⁶, wherein R¹¹⁶ is a C₁-C₁₀alkylgroup, or a tri(C₁-C₈alkyl)silyl group; R¹¹⁷ and R^(117′) are eachindependently C₁-C₂₅alkyl group, which can be substituted one to threetimes with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ areeach independently hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano,C₁-C₂₅alkyl, which may optionally be interrupted by an oxygen or sulphuratom; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; and R¹²² and R^(122′) are eachindependently hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen or sulphur atom; or C₇-C₂₅arylalkyl.
 2. Thepolymer according to claim 1, which is a polymer comprising a unit offormula ⇓Ar¹_(a)YAr^(1′)_(a′) (I′), wherein Y is a group of formula

U¹ is O, S, or NR¹; U² is O, S, or NR²; T¹ and T² are each independentlyhydrogen, halogen, cyano, —COOR¹⁰³, —OCOR¹⁰³, —OR^(103′), C₁-C₂₅alkyl,which may be substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G; R¹ and R² may be the same ordifferent and are each independently selected from the group consistingof hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl,C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl, C₅-C₁₂cycloalkyl, phenyl ornaphthyl which can optionally be substituted with C₁-C₁₂alkyl orC₁-C₁₂alkoxy, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, and—COO—C₁-C₁₈alkyl; a is 1, 2, or 3, a′ is 1, 2, or 3; wherein Ar¹ andAr^(1′) are as defined in claim 1; and R¹⁰³, R^(103′), D, E and G are asdefined in claim
 1. 3. The polymer according to claim 1, comprising atleast one unit selected from the group consisting of formula

wherein U¹ is O, or NR¹; U² is O, or NR²; T¹ and T² are eachindependently hydrogen, or C₁-C₂₅alkyl; R¹ and R² may be the same ordifferent and are each independently selected from a C₁-C₃₈alkyl group;R³ and R^(3′) are each independently hydrogen or C₁-C₂₅alkyl; and R⁸ andR^(8′) are each independently hydrogen or C₁-C₂₅alkyl.
 4. The polymeraccording to claim 3, comprising a unit of formula *A* and *COM¹* ,wherein A is a repeating unit of formula (I), and —COM¹- is a repeatingunit, which has the meaning of Ar², or a group of formula*Ar¹⁴_(s)Ar¹⁵_(t)Ar¹⁶_(u)Ar¹⁷_(v)*, s is 1, t is 1, u is 0, or1, v is 0, or 1, and Ar¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are each independently agroup of formula

 wherein one of X⁵ and X⁶ is N and the other is CR¹⁴, and R¹⁴, R^(14′),R¹⁷ and R^(17′) are each independently H, or a C₁-C₂₅alkyl group.
 5. Thepolymer according to claim 4, wherein A is a repeating unit of formula(Ia), (Ib), (Id), or (Ii), and *COM¹* is a group of formula

where R³, R^(3′), R¹⁷ and R^(17′) are each independently hydrogen, orC₁-C₂₅alkyl.
 6. The polymer according to claim 4, which is a polymer offormula

wherein n is from 4 to 1000, R¹ is a C₁-C₃₈alkyl group, R³, R^(3″) andR^(3′) are each independently hydrogen, halogen, cyano, C₁-C₂₅alkyl orC₁-C₂₅alkoxy; R⁴ and R⁵ are each independently hydrogen, or C₁-C₂₅alkyl;R¹² and R^(12′) are H, or a C₁-C₂₅alkyl group; R⁷ and R^(7′) areindependent of each other; R¹⁴ and R^(14′) are each independentlyhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; R¹⁷ and R^(17′)are each independently H, or a C₁-C₂₅alkyl group; R¹⁰³ is C₁-C₂₅alkyl;R¹⁰⁴ and R^(104′) are each independently hydrogen, cyano, COOR¹⁰³,C₁-C₂₅alkyl; R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are each independentlyhydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; and R¹⁰⁷ isC₁-C₂₅alkyl.
 7. A compound of formulaA¹-YA³-Y¹⁵_(o)A⁴-Y¹⁶_(p)A⁵-Y¹⁷_(q)A² (III), wherein Y, Y¹⁵, Y¹⁶and Y¹⁷ are each independently a group of formula

o is 0, or 1, p is 0, or 1, q is 0, or 1; A¹ and A² are eachindependently a group of formula Ar¹_(a)Ar²_(b)Ar³]_(c)—R¹⁰, A³, A⁴and A⁵ are each independently a group of formula*Ar⁴_(k)Ar⁵₁Ar⁶_(r)Ar⁷_(z)*, k is 1, 2, or 3; 1 is 0, 1, 2, or3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3; R¹⁰ is hydrogen, halogen,cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/orinterrupted by D,

 COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, whichis substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈thioalkoxy,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interruptedby D, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G, or agroup of formulae IVa to IVm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ are each independently H, halogen,cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, aC₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substitutedby G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, orC₇-C₂₅aralkyl, which is substituted by G; R²⁷ and R²⁸ are eachindependently hydrogen, C₁-C₂₅alkyl, halogen, cyano or C₇-C₂₅aralkyl, orR²⁷ and R²⁸ together represent alkylene or alkenylene which may be bothbonded via oxygen and/or sulfur to the thienyl residue and which mayboth have up to 25 carbon atoms; R⁵⁹ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl,which may optionally be interrupted by an oxygen or sulphur atom; orC₇-C₂₅arylalkyl; D is —CO—, —COO—, —S—, —O—, or NR¹¹²—; E isC₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, or halogen;G is E, or C₁-C₁₈alkyl; R¹¹² and R¹¹³ are each independently H;C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;R²¹⁴ and R²¹⁵ are each independently hydrogen, C₁-C₁₈alkyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, —CN or COOR²¹⁶; R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl,C₇-C₂₅arylalkyl, C₆-C₂₄aryl or C₂-C₂₀heteroaryl; Ar⁴, Ar⁵, Ar⁶ and Ar⁷have independently the meaning of Ar¹, or are independently of eachother a group of formula XVa, XVb, XVc, XVd, XVe, XVf, XVg, XVh, XVI, orXVII:

wherein a is 1, 2, or 3; b is 0, 1, 2, or 3; c is 0, 1, 2, or 3; U¹ isO, S, or NR¹; U² is O, S, or NR²; T¹ and T² are each independentlyhydrogen, halogen, hydroxyl, cyano, —COOR¹⁰³, —OCOR¹⁰³, —NR¹¹²COR¹⁰³,—CONR¹¹²R¹¹³, —OR^(103′), —SR^(103′), —SOR^(103′), —SO₂R^(103′),—NR¹¹²SO₂R^(103′), —NR¹¹²R¹¹³, C₁-C₂₅alkyl, which may be substituted byE and/or interrupted by D, C₅-C₁₂cycloalkyl, which can be substitutedone to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy; C₇-C₂₅arylalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G; R¹ and R² may be the same ordifferent and are each independently selected from hydrogen, aC₁-C₁₀₀alkyl group which can optionally be substituted with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group;and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—,NR³⁹CO—, —COO—, —CO— or —OCO—, a C₂-C₁₀₀alkenyl group which canoptionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—, a C₃-C₁₀₀alkinyl group which can optionally besubstituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group,or a siloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—, a C₃-C₁₂cycloalkyl groupwhich can optionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy,halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—, a C₆-C₂₄aryl group which can optionally be substitutedwith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₇-C₂₀heteroaryl, a silyl group, or asiloxanyl group, a C₇-C₂₀heteroaryl group which can optionally besubstituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group,or a siloxanyl group, a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkylgroup, or —COO—C₁-C₁₈alkyl group; R³⁹ is hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl, R¹⁰³ and R^(103′)are each independently C₁-C₁₀₀alkyl, C₁-C₂₅alkyl substituted by E and/orinterrupted with D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G, Ar¹ is

wherein X is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

Ar² Ar³ have independently of each other the meaning of Ar¹, or areindependently of each other

wherein X¹ is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—,—C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are each independently hydrogen, halogen, halogenatedC₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which may optionally be interrupted by an oxygen or sulphur atom;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹⁰⁴ and R^(104′) are eachindependently hydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, orC₆-C₂₄aryl or C₂-C₂₀heteroaryl; R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′)are each independently hydrogen, halogen, halogenated C₁-C₂₅alkyl,especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which mayoptionally be interrupted by an oxygen or sulphur atom; C₇-C₂₅arylalkyl,or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are each independentlyhydrogen, C₁-C₂₅alkyl, which may optionally be interrupted by an oxygen,or sulphur atom; or C₇-C₂₅arylalkyl; R⁸ and R^(8′) are eachindependently hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen or sulphur atom; or C₇-C₂₅arylalkyl; R¹¹ andR^(11′) are each independently C₁-C₂₅alkyl group, which can besubstituted with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are eachindependently hydrogen, halogen, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by an oxygen, orsulphur atom, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or =—R¹³, wherein R¹³ is aC₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; R¹⁰⁴ and R^(104′)are each independently hydrogen, C₁-C₁₈alkyl, C₆₋₁₀aryl, which mayoptionally be substituted by G, or C₂-C₈heteroaryl, which may optionallybe substituted by G; R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are eachindependently hydrogen, halogen, cyano, C₁-C₂₅alkyl, which mayoptionally be interrupted by an oxygen or sulphur atom; C₇-C₂₅arylalkyl,or C₁-C₁₈alkoxy; R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈perfluoroalkyl; C₁-C₂₅alkyl, which may be interrupted by —O—, or—S—; or —COOR¹⁰³; R¹⁰⁸ and R¹⁰⁹ are each independently H, C₁-C₂₅alkyl,C₁-C₂₅alkyl which is substituted by E and/or interrupted by D,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₁-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₇-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁸ andR¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹are each independently H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six memberedring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₇-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl, R¹¹² and R¹¹³ are each independently H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, R¹¹⁴ isC₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally be interruptedby an oxygen, or sulphur atom, R¹¹⁵ and R^(115′) are each independentlyhydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen, or sulphur atom, C₁-C₂₅alkoxy, C₇₋₅arylalkyl,or =—R¹¹⁶, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or atri(C₁-C₈alkyl)silyl group; R¹¹⁷ and R^(117′) are each independentlyC₁-C₂₅alkyl group, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are eachindependently hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano,C₁-C₂₅alkyl, which may optionally be interrupted by an oxygen or sulphuratom; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; and R¹²² and R^(122′) are eachindependently hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen or sulphur atom; or C₇-C₂₅arylalkyl.
 8. Thecompound according to claim 7, which is a compound of formula

wherein A¹, A², A³, A⁴, A⁵, T¹, T², U¹ and U² are as defined in claim 7,T^(1′), T^(2′), T^(1″), T^(2″), T^(1*) and T^(2*) each independentlyhave the meaning of T¹, and U^(1′), U^(2′), U^(1″), U^(2″), U^(1*) andU^(2*) each independently have the meaning of U¹.
 9. An organicsemiconductor material, layer or component, comprising a polymeraccording to claim
 1. 10. A semiconductor device, comprising a polymeraccording to claim
 1. 11. The semiconductor device according to claim10, which is an organic photovoltaic device, a photodiode, or an organicfield effect transistor.
 12. A process for preparation of an organicsemiconductor device, the process comprising: applying a solution, adispersion, or both of a compound according to claim 7 in an organicsolvent to a suitable substrate; and removing the solvent; or theprocess comprising evaporation of the compound according to claim
 7. 13.The polymer according to claim 1, wherein the polymer is suitable for PVdevices, photodiodes, as IR absorber, or organic field effecttransistor.
 14. A compound of formula X²Ar³_(c)Ar²_(b)Ar¹_(a)YAr^(1′)_(a′)Ar^(2′)_(b′)Ar^(3′)_(c′)X^(2′) (V), wherein Y is agroup of formula

a is 1, 2, or 3, a′ is 1, 2, or 3; b is 0, 1, 2, or 3; b′ iso, 1, 2, or3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; U¹ is O, S, or NR¹; U² is O,S, or NR²; T¹ and T² are each independently hydrogen, halogen, hydroxyl,cyano, —COOR¹⁰³, —OCOR¹⁰³, —NR¹¹²COR¹⁰³, —CONR¹¹²R¹¹³, —OR^(103′),—SR^(103′), —SOR^(103′), —SO₂R^(103′), —NR¹¹²SO₂R^(103′), —NR¹¹²R¹¹³,C₁-C₂₅alkyl, which may be substituted by E and/or interrupted by D,C₅-C₁₂cycloalkyl, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl whichis substituted by G; R¹ and R² may be the same or different and are eachindependently selected from hydrogen, a C₁-C₁₀₀alkyl group which canoptionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—, a C₇-C₁₀₀alkenyl group which can optionally besubstituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group,or a siloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—, a C₃-C₁₀₀alkinyl groupwhich can optionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy,halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group; and/or canoptionally be interrupted by —O—, —S—, —NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—,—CO— or —OCO—, a C₃-C₁₂cycloalkyl group which can optionally besubstituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl,nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group,or a siloxanyl group; and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, CONR³⁹—, NR³⁹CO—, —COO—, —CO— or —OCO—, a C₆-C₂₄aryl group whichcan optionally be substituted with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen,C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, a silyl group, or a siloxanyl group, aC₂-C₂₀heteroaryl group which can optionally be substituted withC₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group, or asiloxanyl group; a —CO—C₁-C₁₈alkyl group, a —CO—C₅-C₁₂cycloalkyl group,or —COO—C₁-C₁₈alkyl group; R³⁹ is hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl; R¹⁰³ and R^(103′)are each independently C₁-C₁₀₀alkyl, C₁-C₂₅alkyl substituted by E and/orinterrupted with D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G; Ar¹ and Ar^(1′) are each independently

wherein X is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

Ar², Ar^(2′), Ar³ and Ar^(3′) have independently of each other themeaning of Ar¹, or are independently of each other

wherein X¹ is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—,—C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are each independently hydrogen, halogen, halogenatedC₁-C₂₅alkyl, especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl,which may optionally be interrupted by an oxygen or sulphur atom;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹⁰⁴ and R^(104′) are eachindependently hydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, orC₆-C₂₄aryl or C₂-C₂₀heteroaryl; R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′)are each independently hydrogen, halogen, halogenated C₁-C₂₅alkyl,especially CF₃, cyano, C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which mayoptionally be interrupted by an oxygen or sulphur atom; C₇-C₂₅arylalkyl,or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are each independentlyhydrogen, C₁-C₂₅alkyl, which may optionally be interrupted by an oxygen,or sulphur atom; or C₇-C₂₅arylalkyl; R⁸ and R^(8′) are eachindependently hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen or sulphur atom; or C₇-C₂₅arylalkyl; R¹¹ andR^(11′) are each independently C₁-C₂₅alkyl group, which can besubstituted with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are eachindependently hydrogen, halogen, cyano, C₁-C₂₅alkyl, especiallyC₃-C₂₅alkyl, which may optionally be interrupted by an oxygen, orsulphur atom, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or =—R¹³, wherein R¹³ is aC₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; R¹⁰⁴ and R^(104′)are each independently hydrogen, C₁-C₁₈alkyl, C₆-C₁₀aryl, which mayoptionally be substituted by G, or C₂-C₈heteroaryl, which may optionallybe substituted by G; R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are eachindependently hydrogen, halogen, cyano, C₁-C₂₅alkyl, which mayoptionally be interrupted by an oxygen or sulphur atom; C₇-C₂₅arylalkyl,or C₁-C₁₈alkoxy; R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈perfluoroalkyl; C₁-C₂₅alkyl, which may be interrupted by —O—, or—S—; or —COOR¹⁰³; R¹⁰⁸ and R¹⁰⁹ are each independently H, C₁-C₂₅alkyl,C₁-C₂₅alkyl which is substituted by E and/or interrupted by D,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₇-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁸ andR¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹are each independently H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six memberedring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₇-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl; D is —CO—, —COO—, —S—, —O—, or NR¹¹²—; E isC₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, or halogen;G is E, or C₁-C₁₈alkyl; R¹¹² and R¹¹³ are each independently H;C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈ alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R¹¹⁴ is C₁-C₂₅alkyl, especially C₃-C₂₅alkyl, which may optionally beinterrupted by an oxygen, or sulphur atom; R¹¹⁵ and R^(115′) are eachindependently hydrogen, halogen, cyano, C₁-C₂₅alkyl, which mayoptionally be interrupted by an oxygen, or sulphur atom, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or =—R¹¹⁶, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or atri(C₁-C₈alkyl)silyl group; R¹¹⁷ and R^(117′) are each independentlyC₁-C₂₅alkyl group, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are eachindependently hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano,C₁-C₂₅alkyl, which may optionally be interrupted by an oxygen or sulphuratom; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹²² and R^(122′) are eachindependently hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by an oxygen or sulphur atom; or C₇-C₂₅arylalkyl; and X² andX^(2′) are each independently halogen, ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, whereinR²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are eachindependently H or C₁-C₆alkyl, wherein two radicals optionally form acommon ring and these radicals are optionally branched or unbranched andX¹² is a halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂,—B(OY¹)₂,

 —BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group and Y¹³ and Y¹⁴ are each independently hydrogen, ora C₁-C₁₀alkyl group.
 15. A process for the preparation of a polymer offormula

according to claim 4, comprising reacting a dihalogenide of formulaX¹⁰-A-X¹⁰ with an equimolar amount of a diboronic acid or diboronatecorresponding to formula, or X¹¹COM¹X¹¹, or reacting a dihalogenide offormula X¹⁰COM¹X¹⁰ with an equimolar amount of a diboronic acid ordiboronate corresponding to formula X¹¹-A-X¹¹, wherein X¹⁰ is halogen,and X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂,

 wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group and Y¹³and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkylgroup, in a solvent and in the presence of a catalyst; or reacting adihalogenide of formula X¹⁰-A-X¹⁰ with an equimolar amount of an organotin compound corresponding to formula X^(11′)COM¹X^(11′), or reactinga dihalogenide of formula X¹⁰COM¹X¹⁰ with an equimolar amount of anorgano tin compound corresponding to formula X^(11′)-A-X^(11′), whereinX^(11′) is independently in each occurrence —SnR²⁰⁷R²⁰⁸R²⁰⁹, whereinR²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl,or two of the groups R²⁰⁷, R²⁰⁸ and R²⁰⁹ form a ring and these groupsare optionally branched, A and COM¹ are as defined in claim 4 and n isin the range of 4 to
 1000. 16. A polymer comprising the compoundaccording to claim 7, which is a repeating unit of formula

wherein A^(1′) and A^(2′) are independently of each other a group offormula

 wherein a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴ and A⁵are as defined in claim
 7. 17. A process for the preparation of acompound according to claim 7, which is a compound of formula

comprising a) reacting one to three equivalents of a ketoamide offormula

 with one equivalent of a 1,4-cyclohexanedione of the formula

 in the presence of a base in a solvent, whereby an intermediate productof the formula

 is obtained, and b) treating the intermediate product of the formula(IX) with an acid to obtain a compound of formula (IIIa′), wherein R¹,T¹, T², and A¹ are as defined in claim
 7. 18. A process for thepreparation of a compound according to claim 7, which is a compound offormula

comprising a) reacting one to three equivalents of a ketoamide offormula

 with one equivalent of a 1,2-cyclohexanedione of the formula

 in the presence of a base in a solvent, whereby an intermediate productof the formula

 is obtained, and b) treating the intermediate product of the formula(VIII) with an acid to obtain a compound of formula (Me), wherein R¹,T¹, T², and A¹ are as defined in claim
 7. 19. A 1,4-cyclohexanedione offormula

which is suitable for preparation of a compound according to claim 7,which is a compound of formula

wherein R¹, T¹, T², and A¹ are as defined in claim
 7. 20. A1,2-cyclohexanedione of formula

which is suitable for preparation of a compound according to claim 7,which is a compound of formula

wherein R¹, T¹, T², and A¹ are as defined in claim 7.